JP6571205B2 - Polyetherimide miscible polymer blends for capacitor films - Google Patents

Description

  The present disclosure relates to polyetherimide miscible polymer blends, and methods of making and using the same, and more particularly, polyetherimide and / or polyetherimide sulfone miscible polymer blends for extruded capacitor films.

  With high capacity energy density, high operating temperature and long life, electrostatic film capacitors are important components for pulse power, automotive and industrial electronics. In general, a capacitor is an energy storage device having two parallel conductive plates separated by a thin layer of insulating (dielectric) film. When a voltage is applied between these plates, the electric field in the dielectric moves the charge and thus stores energy. The amount of energy stored by the capacitor depends on the dielectric constant of the insulating material, applied voltage, and film dimensions (total area and thickness). Therefore, in order to maximize the total amount of energy that the capacitor can store, the dielectric constant and breakdown voltage of the film must be maximized and the thickness of the film must be minimized. The physical nature of the dielectric material in the capacitor is a primary determinant on the performance of the capacitor, so improving one or more of the physical properties of the capacitor dielectric material will result in a corresponding performance of the capacitor component. Can be improved, thus enhancing the performance and lifetime of the electronic system or product in which the capacitor is typically embedded.

US Pat. No. 8,546,516 US Patent Application Publication No. 2014/0355173 US Pat. No. 6,919,422 US Pat. No. 6,072,011 US Patent Application Publication No. 2014/0179843

  Electrostatic film capacitors made from biaxially oriented poly (propylene) (BOPP) have low dielectric loss tangents, high insulation resistivity, and electrical equipment, electronic devices, ovens and furnaces, refrigerators, automobiles, and home appliances, etc. It has been used for applications that require low dielectric absorption. The low relative permittivity (Dk) of BOPP, which is about 2.2, and the maximum operating temperature of BOPP of about 100 ° C. make it possible to use BOPP capacitors in applications where high operating temperatures and / or high energy densities are required. Limited. Other thermoplastic materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polycarbonate (PC) with Dk> 3.0 may be a reasonable alternative. However, capacitors made from these films can only be used at operating temperatures as high as about 125 ° C. and therefore do not meet the desired high temperature performance capability. Some materials that respond to high temperature capability, such as polyphenylene sulfide (PPS) and polyetheretherketone (PEEK), are limited by unstable electrical properties at temperatures above 150 ° C., thus, PPS and PEEK Is less desirable for use in capacitors. Accordingly, there is a continuing need to develop and / or improve dielectric materials for use in capacitors.

  A uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide and poly (carbonate-arylate ester), the polyetherimide comprising an aromatic dianhydride and m-phenylenediamine , Including units derived from polymerization with diamines, including p-phenylenediamines or combinations thereof, end-capped with substituted or unsubstituted aromatic primary monoamines, and the poly (carbonate-arylate esters) are different from each other The high yield extruded capacitor film comprising bisphenol carbonate repeat units and arylate ester repeat units, based on the total weight of the miscible polymer blend prior to entering the extruder used to produce the capacitor film, Extrusion Comprising about 90% or more by weight of the miscible polymer blend enters the uniaxial stretching high yield extrusion capacitor film is disclosed herein.

  Similarly, a uniaxially stretched high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide and poly (carbonate-arylate ester), the polyetherimide comprising an aromatic dianhydride, m -Containing units derived from polymerization with diamines including phenylenediamine, p-phenylenediamine or combinations thereof, end-capped with a substituted or unsubstituted aromatic primary monoamine, wherein the poly (carbonate-arylate ester) is The high-yield extruded capacitor film comprising different bisphenol carbonate repeating units and arylate ester repeating units is solvent-free and miscible before entering the extruder used to produce the capacitor film Polymer blend Uniaxially stretched, high-yield extruded capacitor film comprising about 90% by weight or more of the miscible polymer blend entering the extruder and having a film thickness of about 0.1 microns to about 20 microns, based on total weight Are also disclosed herein.

  Further, a uniaxially stretched high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide sulfone and poly (carbonate-arylate ester), wherein the polyetherimide sulfone comprises an aromatic dianhydride, The poly (carbonate-arylate ester) contains units derived from polymerization with a diamine containing diaminodiphenylsulfone and is end-capped with a substituted or unsubstituted aromatic primary monoamine, wherein the poly (carbonate-arylate ester) comprises bisphenol carbonate repeating units and arylates that are different from each other. The high-yield extruded capacitor film comprising ester repeat units is solvent-free and is based on the total weight of the miscible polymer blend before entering the extruder used to make the capacitor film, Extrusion Comprising about 90% or more by weight of the miscible polymer blend enters the uniaxial stretching high yield extrusion capacitor film is disclosed.

  For a detailed description of preferred embodiments of the disclosed compositions and methods of making and using them, reference will now be made to the accompanying drawings in which:

2 is a graph of the average breaking strength (BDS) of a polymer composition for a capacitor film, measured on a 10 micron film sample, compared to a control sample. FIG. 3 is a graph of the average BDS of a polymer composition for a capacitor film, measured on a 20 micron film sample, compared to a control sample.

  Disclosed herein are polymer compositions for capacitor films comprising polyetherimide (PEI) and polycarbonate (PC), as well as methods for making and using the same, the polymer compositions being described in more detail herein. Discussed miscible polymer blends. In one embodiment, the polyetherimide can further comprise a polyetherimide sulfone, the polyetherimide and the polyetherimide sulfone forming a miscible polymer blend. In one embodiment, the polycarbonate comprises poly (carbonate-arylate ester). In one embodiment, the polyetherimide and polycarbonate form a miscible polymer blend. In another embodiment, the polyetherimide, polyetherimide sulfone, and polycarbonate form a miscible polymer blend.

  In some embodiments, the polymer composition for the capacitor film comprises polyetherimide sulfone (PEIS) and polycarbonate (PC), the polymer composition being a miscible polymer blend. In such embodiments, the polyetherimide sulfone and the polycarbonate form a miscible polymer blend.

  A uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide and poly (carbonate-arylate ester), the polyetherimide comprising an aromatic dianhydride and m-phenylenediamine , Including units derived from polymerization with diamines, including p-phenylenediamines or combinations thereof, end-capped with substituted or unsubstituted aromatic primary monoamines, and the poly (carbonate-arylate esters) are different from each other The high yield extruded capacitor film comprising bisphenol carbonate repeat units and arylate ester repeat units, based on the total weight of the miscible polymer blend prior to entering the extruder used to produce the capacitor film, Extrusion Comprising about 90% or more by weight of the miscible polymer blend enters the uniaxial stretching high yield extrusion capacitor film is disclosed herein. In one embodiment, the polyetherimide can further comprise polyetherimide sulfone.

  In one embodiment, a method of making a uniaxially stretched high yield extruded capacitor film, such as the film described in the preceding paragraph, comprises (a) combining polyetherimide and poly (carbonate-arylate ester) and blending. Forming a miscible polymer blend; (b) melting and mixing the miscible polymer blend to form a molten polymer; (c) filtering the molten polymer to remove particles greater than about 1 micron. Forming a filtered molten polymer, and (d) extruding the filtered molten polymer with a flat die at a temperature of about 250 ° C. to about 500 ° C. to form a high yield extruded capacitor film. The high yield extruded capacitor film for producing the capacitor film. A step comprising: greater than about 90% by weight of the miscible polymer blend entering the extruder, based on the total weight of the miscible polymer blend prior to entering the extruder used; and (e) the high yield extrusion Uniaxially stretching the molded capacitor film to form a uniaxially stretched, high yield extruded capacitor film. In such an embodiment, the uniaxially stretched, high yield extruded capacitor film can be further metallized and wound to form a wound metallized capacitor film. In another embodiment, the capacitor film (eg, a metallized capacitor film) can be laminated to form a laminated film capacitor.

  A uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide sulfone and poly (carbonate-arylate ester), wherein the polyetherimide sulfone comprises an aromatic dianhydride and diaminodiphenyl The poly (carbonate-arylate ester) contains units derived from polymerization with a sulfone-containing diamine and is end-capped with a substituted or unsubstituted aromatic primary monoamine, the poly (carbonate-arylate ester) being a different bisphenol carbonate repeating unit and arylate ester repeating The high yield extruded capacitor film comprising units, wherein the miscibility entering the extruder is relative to the total weight of the miscible polymer blend prior to entering the extruder used to produce the capacitor film. polymer Comprising about 90 wt% or more trends, uniaxial stretching high yield extrusion capacitor film is disclosed herein.

  In one embodiment, a method of producing a uniaxially stretched high yield extruded capacitor film, such as the film described in the above paragraph, comprises (a) combining polyetherimide sulfone and poly (carbonate-arylate ester): Forming a miscible polymer blend; (b) melting and mixing the miscible polymer blend to form a molten polymer; and (c) filtering the molten polymer to remove particles greater than about 1 micron. Step (d) of extruding the filtered molten polymer with a flat die at a temperature of about 250 ° C. to about 500 ° C. to form a high yield extruded capacitor film. And the high yield extruded capacitor film produces the capacitor film. Comprising, over the total weight of the miscible polymer blend prior to entering the extruder used to comprise about 90% by weight or more of the miscible polymer blend entering the extruder, and (e) the high yield Uniaxially stretching the rate-extruded capacitor film to form a uniaxially stretched, high-yield extruded capacitor film. In such an embodiment, the uniaxially stretched high yield extruded capacitor film can be further metallized and wound to form a wound metallized capacitor film. In another embodiment, a capacitor film (eg, a metallized capacitor film) can be laminated to form a laminated film capacitor.

  Unless otherwise indicated in the working examples or where indicated, all numbers or expressions referring to the amounts of ingredients, reaction conditions, etc., as used in the specification and claims are used in all cases. Should be understood as being modified by the term “about”. Various numbers of ranges are disclosed herein. Since these ranges are continuous, they include each value between the minimum and maximum values. All ranges of extreme values listing the same property or component may be combined independently and include the listed extreme values. Unless expressly indicated otherwise, the various number ranges specified in this application are approximate. All endpoints of the range that cover the same component or characteristic include this endpoint and can be combined independently. The term “from greater than 0 to an amount” means that the specified component is present in an amount greater than 0, as well as in a maximum amount, including the higher specified amount.

  The terms “a”, “an” and “the” do not represent a quantity limitation, but rather indicate that at least one of the referenced items is present. As used herein, the singular forms “a”, “an”, and “the” include plural referents.

  As used herein, “a combination thereof” includes one or more of the listed elements, optionally with similar elements not listed, eg, one of the specified constituents. Includes a combination of a species or a plurality and optionally one or more other components not specifically specified that have essentially the same function. As used herein, the term “combination” includes blends, mixtures, alloys, reaction products, and the like.

  Throughout this specification, references to “one embodiment,” “another embodiment,” “other embodiments,” “some embodiments,” and the like are specific to the embodiment described in connection with the embodiment. Elements (eg, features, structures, properties and / or properties) are included in at least one embodiment described herein, and may or may not be present in other embodiments. It means that you do n’t have to. Furthermore, the described elements may be combined in any suitable manner in various embodiments.

  Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The term “polymer” as used herein includes oligomers, homopolymers and copolymers.

  All molecular weights in this application refer to weight average molecular weight unless otherwise indicated. The molecular weight so mentioned is expressed in Daltons (Da).

  Compounds are described herein using standard nomenclature. For example, any position not substituted by any indicated group is understood to have a valence occupied by the indicated bond, or a hydrogen atom. A dash “-” that does not exist between two letters or symbols is used to indicate the point of attachment of the substituent. For example, -CHO is bonded through the carbon of the carbonyl group.

The term “alkyl” includes both branched and straight chain C _1-30 , or both branched and straight chain C _1-18 saturated aliphatic hydrocarbon groups having the specified number of carbon atoms. including. Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl. N- and s-heptyl, n- and s-octyl, decyl, stearyl and the like.

The term “alkenyl” refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond (eg, ethenyl (HC═CH ₂ )), straight or branched.

The term “alkoxy” refers to a straight or branched alkyl group (eg, C _1-18 ) (ie, alkyl-O—), such as methoxy, ethoxy, sec-butyloxy and nonyloxy groups, linked through oxygen. means.

The term “alkylene” means a linear or branched, saturated divalent aliphatic hydrocarbon group (eg, methylene (—CH ₂ —) or propylene (— (CH ₂ ) ₃ —)).

The term “cycloalkylene” refers to the divalent cyclic alkylene group —C _n H _2n-x , where x represents the number of hydrogens replaced by cyclization. “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (eg, cyclopentyl and Cyclohexyl).

  The term “aryl” means an aromatic hydrocarbon group (eg, an aromatic moiety) containing the specified number of carbon atoms (eg, an unsaturated ring of 6 carbon atoms), which group It may be optionally substituted by one or more alkyl groups and includes, for example, phenyl, tolyl, xylyl, tropone, indanyl, indenyl, naphthyl and the like.

  The term “aryloxy” means an oxygen radical substituted by an unsaturated ring of 6 carbon atoms, which radical may be optionally substituted by one or more alkyl groups, for example , Including phenoxy.

  The prefix “halo” means a group or compound that further comprises one fluoro, chloro, bromo, iodo, and astatino substituent. There may be a combination of different halo groups (eg, bromo and fluoro). In one embodiment, only chloro groups are present.

  The prefix “hetero” includes at least one ring member in which the compound or group is a heteroatom (eg, 1, 2 or 3 heteroatoms), each heteroatom independently being N , O, S or P.

  All ASTM tests are based on the 2003 edition of Annual Book of ASTM Standards unless otherwise indicated.

  In one embodiment, the polymer composition for a capacitor film includes a polyetherimide. In another embodiment, the capacitor film polymer composition comprises polyetherimide sulfone. In yet another embodiment, the capacitor film polymer composition comprises polyetherimide and polyetherimide sulfone.

  For the purposes of the disclosure herein, a polymer component comprising either polyetherimide alone or polyetherimide sulfone, or both polyetherimide and polyetherimide sulfone, is “polyetherimide and / or polyimide”. Collectively called “etherimide sulfone”. As used herein with respect to any of the described polymers (eg, single polymer components, polymer blends, polymer blends, etc.), properties, properties, characteristics, etc., the term “polyetherimide and / or polyether” “Imidosulfone” is a property of polyetherimide and polyetherimide sulfone when any of the property values, properties, characteristics, etc. is used in either polyetherimide or polyetherimide sulfone alone or in combination. Both can apply.

（式中、ａは、１超、例えば、約１〜約１，０００以上、あるいは約１０〜約１，０００以上、またはあるいは約１０〜約５００とすることができる）
によって表すことができる。 In one embodiment, the polyetherimide (PEI) and polyetherimide sulfone (PEIS) have the formula I:

Wherein a can be greater than 1, for example, from about 1 to about 1,000 or more, alternatively from about 10 to about 1,000 or more, or alternatively from about 10 to about 500.
Can be represented by

  In one embodiment, the group V in formula I is a tetravalent linker containing an ether group (“polyetherimide” as used herein), or a combination of an ether group and an arylene sulfone group (herein When used in writing, it can be “polyetherimide sulfone”). Such linkers include, but are not limited to, (a) substituted or unsubstituted monocyclic and polycyclic saturated, unsaturated or aromatic groups having 5 to 50 carbon atoms. A saturated, unsaturated or aromatic group, optionally substituted by an ether group, an arylene sulfone group, or a combination of an ether group and an arylene sulfone group, (b) 1-30 carbon atoms A substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl group, an ether group, or a combination of an ether group and an arylene sulfone group, and an alkyl optionally substituted with an arylene sulfone group Groups, or (c) combinations thereof may be included. Further substituents suitable for linker group V include, but are not limited to, ethers, amides, esters, etc., or combinations thereof.

（式中、Ｑ^１は、以下に限定されないが、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−ＳＯ_２−、−ＳＯ−、−Ｃ_ｙ〜２ｙ−などの二価部分（ｙは、１〜５の整数である）、およびペルフルオロアルキレン基を含めた、このハロゲン化誘導体を含む）により表される、二価の基などの、置換または無置換の二価有機基を含むことができる。 In one embodiment, the group R in formula I includes, but is not limited to, (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a halogenated derivative thereof, (b) 2 to 20 (C) a cycloalkylene group having 3 to 20 carbon atoms, or (d) Formula II:

(In the formula, Q ¹ is not limited to the following, but a divalent moiety such as —O—, —S—, —C (O) —, —SO ₂ —, _—SO— , —C _{y to 2y} —) ( y is an integer from 1 to 5), and includes substituted or unsubstituted divalent organic groups, such as divalent groups, including halogenated derivatives including perfluoroalkylene groups) be able to.

（式中、Ｗは、−Ｏ−、−ＳＯ_２−を含めた二価部分、または式−Ｏ−Ｚ−Ｏ−により表される基とすることができ、−Ｏ−または−Ｏ−Ｚ−Ｏ−基の二価結合は、３，３’、３，４’、４，３’、または４，４’位にあることができる）により表される、四価芳香族基を含む。当業者により認識されている通り、および本開示の一助により−Ｏ−Ｚ−Ｏ−基は二価の基である一方、Ｚもやはり二価の基であり、Ｚの二価はそれぞれ、−Ｏ−Ｚ−Ｏ−基中の酸素原子に連結している。このような実施形態では、Ｚは、以下に限定されないが、基ＩＶの式：

（式中、Ｑは、以下に限定されないが、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−ＳＯ_２−、−ＳＯ−、−Ｃ_ｙ〜２ｙ−などの二価部分（ｙは、１〜５の整数である）、およびペルフルオロアルキレン基を含めた、このハロゲン化誘導体を含むことができる）により表される二価の基を含むことができる。 In one embodiment of Formula I, the linker V is not limited to:

Wherein W can be a divalent moiety including —O—, —SO ₂ —, or a group represented by the formula —O—Z—O—, —O— or —O—Z The divalent bond of the —O— group comprises a tetravalent aromatic group represented by: 3,3 ′, 3,4 ′, 4,3 ′, or 4,4 ′. As recognized by those skilled in the art and with the aid of the present disclosure, the —O—Z—O— group is a divalent group, while Z is also a divalent group, where the divalent value of Z is — It is connected to the oxygen atom in the O—Z—O— group. In such embodiments, Z is, but is not limited to, the formula of group IV:

(In the formula, Q is not limited to the following, but a divalent moiety such as —O—, —S—, —C (O) —, —SO ₂ —, _—SO— , —C y to _2y —) Is an integer from 1 to 5), and can include halogenated derivatives thereof, including perfluoroalkylene groups).

（式中、Ｑ^ａは、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−ＳＯ_２−、−ＳＯ−または−Ｃ_ｙ〜２ｙ−、このハロゲン化誘導体とすることができ、ｙは、１〜５の整数とすることができる）により表される、二価の基とすることができる。 In one embodiment, Z is of formula IVa:

(In the formula, Q ^a is a single bond, —O—, —S—, —C (O) —, —SO ₂ —, _—SO— , or —C _{y to 2 y} —, a halogenated derivative thereof). And y can be an integer from 1 to 5).

（式中、Ｔは、−Ｏ−、または式−Ｏ−Ｚ−Ｏ−により表される基とすることができ、−Ｏ−または−Ｏ−Ｚ−Ｏ−基の二価結合は、３，３’、３，４’、４，３’、または４，４’位にあることができ、Ｚは、基ＩＶの式および式ＩＶａにより表される、二価の基として本明細書において既に記載されており、Ｒは、式ＩＩにより表される二価の基として、本明細書において既に記載されている）により表すことができる。このようなＺおよびＲの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＶのＺ基およびＲ基を記載することができる。一実施形態では、Ｚは、式ＩＶａにより表すことができる。 In one embodiment, the polyetherimide comprises more than one more structural unit, alternatively from about 10 to about 1,000 structural units, alternatively from about 10 to about 500 structural units, Is the formula V:

(In the formula, T can be —O— or a group represented by the formula —O—Z—O—, and the divalent bond of the —O— or —O—Z—O— group is 3 , 3 ′, 3,4 ′, 4,3 ′, or 4,4 ′, where Z is a divalent group represented by the formula of group IV and formula IVa as used herein. Have already been described, and R can be represented by the divalent group represented by Formula II as already described herein). Any of the described aspects and / or embodiments of Z and R can be utilized in a non-limiting manner to describe the Z and R groups of formula V. In one embodiment, Z can be represented by Formula IVa.

In one embodiment of formula V, wherein T is represented by the formula —O—Z—O—, Z is a divalent aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenated derivative thereof, 2 to A linear or branched alkylene group having 10 carbon atoms, a halogenated derivative thereof, a cycloalkylene group having 3 to 20 carbon atoms, a halogenated derivative thereof, or by the formula — (C ₆ H ₁₀ ) _z — And z can be an integer from 1 to 4, and R can be a diamine residue comprising m-phenylenediamine, p-phenylenediamine, or a combination thereof. it can.

  In another embodiment, the polyetherimide sulfone can be a polyimide comprising an ether group and a sulfone group, and at least 50 mol% of the linker V and group R in Formula I comprises a divalent arylene sulfone group. For example, all linkers V, not the group R, can contain an arylene sulfone group. All R groups, not the linker V, can contain an arylene sulfone group. Alternatively, arylene sulfone can be present in certain portions of the linker V and R groups, provided that the total mole fraction of V and R groups containing aryl sulfone groups is 50 mol% or more and To do.

（式中、Ｙは、−Ｏ−、−ＳＯ_２−、または式−Ｏ−Ｚ−Ｏ−により表される基とすることができ、−Ｏ−、−ＳＯ_２−または−Ｏ−Ｚ−Ｏ−基の二価結合は、３，３’、３，４’、４，３’、または４，４’位にあることができ、Ｚは、基ＩＶの式および式ＩＶａにより表される二価の基として、本明細書において既に記載されており、Ｒは、式ＩＩにより表される二価の基として、本明細書において既に記載されているが、但し、式ＶＩ中のＹのモル数＋Ｒのモル数の合計の５０ｍｏｌ％超が、−ＳＯ_２−基を含有する条件とする）によって表すことができる。このようなＺおよびＲの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＶＩのＺ基およびＲ基を記載することができる。一実施形態では、Ｚは、式ＩＶａにより表すことができる。 In one embodiment, the polyetherimide sulfone comprises more than one structural unit, alternatively from about 10 to about 1,000 structural units, alternatively from about 10 to about 500 structural units, wherein the structural unit is of formula VI:

Wherein Y can be a group represented by —O—, —SO ₂ —, or a formula —O—Z—O—, —O—, —SO ₂ — or —O—Z— The divalent bond of the O-group can be in the 3,3 ′, 3,4 ′, 4,3 ′, or 4,4 ′ position, Z is represented by the formula of group IV and formula IVa As already described herein as a divalent group, R is already described herein as a divalent group represented by formula II, provided that Y in formula VI More than 50 mol% of the total number of moles of the number of moles + R can be expressed as a condition containing a —SO ₂ — group. Any of the described aspects and / or embodiments of Z and R can be utilized in a non-limiting manner to describe the Z and R groups of formula VI. In one embodiment, Z can be represented by Formula IVa.

により表されるリンカーなどの、エーテル基、またはエーテル基およびスルホン基を含まない、リンカーＶをさらに含むことができる。 In some embodiments, the polyetherimide and / or polyetherimide sulfone is, for example, a group of formula VII:

A linker V that does not contain an ether group, or an ether group and a sulfone group, such as a linker represented by

  In one embodiment, the imide unit-containing linker represented by the formula of group VII is generally present in an amount ranging from about 0 mol% to about 10 mol% total units, or alternatively from 0 mol% to 5 mol% total units. can do. In one embodiment, there is no additional linker V in the polyetherimide and / or polyetherimide sulfone.

  In yet another embodiment, the polyetherimide comprises from about 10 to about 500 structural units represented by Formula V, and the polyetherimide sulfone comprises from about 10 to about 500 structural units represented by Formula VI. Including.

  Methods for preparing polyetherimides and polyetherimide sulfones are known to those skilled in the art and are generally described in US Pat. It is.

を、式Ｘにより表される有機ジアミン

と反応させることによって調製することができ、式中、Ｒ、ＴおよびＹは、式ＩＩ、式Ｖおよび式ＶＩについて、本明細書に既に記載されている。このようなＲ、ＴおよびＹの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＶＩＩＩ、式ＩＸおよび式ＸのＲ基、Ｔ基およびＹ基を記載することができる。 In one embodiment, the polyetherimide and polyetherimide sulfone are aromatic dianhydrides represented by Formula VIII or Formula IX

An organic diamine represented by formula X

Wherein R, T and Y have already been described herein for formula II, formula V and formula VI. Any of the described aspects and / or embodiments of R, T and Y are used in a non-limiting manner to describe the R, T and Y groups of formula VIII, formula IX and formula X. Can do.

  Non-limiting examples of aromatic dianhydrides suitable for use in the present disclosure represented by Formula VIII are 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4′-bis (3,4 -Dicarboxyphenoxy) benzophenone dianhydride; 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether Dianhydride; 4,4′-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4′-bis (2,3-dicarboxyphenoxy) Benzophenone dianhydride; 4- (2,3-dicarboxyphenoxy) -4 ′-(3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 4- (2,3-dicarboxyphenoxy) ) -4 ′-(3,4-dicarboxyphenoxy) diphenyl ether dianhydride; 4- (2,3-dicarboxyphenoxy) -4 ′-(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4 -(2,3-dicarboxyphenoxy) -4 '-(3,4-dicarboxyphenoxy) benzophenone dianhydride and the like; or combinations thereof.

  Non-limiting examples of sulfone group-containing aromatic dianhydrides represented by Formula IX suitable for use in the present disclosure include 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4′-bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4- (2,3-dicarboxyphenoxy) -4 ′-(3,4-dicarboxyphenoxy) diphenylsulfone dianhydride Etc .; or combinations thereof.

  In one embodiment, the polyetherimide sulfone can be prepared using a combination of dianhydrides represented by Formula VIII and Formula IX.

  Non-limiting examples of amine compounds represented by Formula X suitable for use in the present disclosure include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nona Methylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxy Xamethylenediamine, 1,2-bis (3-aminopropoxy) ethane, bis (3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis- (4-aminocyclohexyl) methane, m-phenylenediamine, p- Phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl -4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis (4-aminophenyl) methane, bis (2-chloro-4-amino-3,5-diethylphenyl) methane, bis (4-aminophenyl) Nyl) propane, 2,4-bis (b-amino-t-butyl) toluene, bis (p-b-amino-t-butylphenyl) ether, bis (p-b-methyl-o-aminophenyl) benzene, Bis (p-b-methyl-o-aminopentyl) benzene, 1,3-diamino-4-isopropylbenzene, bis (4-aminophenyl) ether, 1,3-bis (3-aminopropyl) tetramethyldisiloxane Or a combination thereof.

  Non-limiting examples of sulfone group-containing amine compounds represented by Formula X suitable for use in the present disclosure include diaminodiphenyl sulfone (DDS), 4,4′-diaminodiphenyl sulfone (4,4′-DDS), 3 , 3′-diaminodiphenylsulfone (3,3′-DDS), bis (aminophenoxyphenyl) sulfone (BAPS), etc., or combinations thereof.

により表される二価の基とすることができる。 In one embodiment, the polyetherimide includes structural units represented by Formula V, each R can independently be p-phenylene, m-phenylene, or a combination thereof, where T is the formula The divalent bond of the —O—Z—O— group can be in the 3,3 ′ position, and Z is the formula XI:

It can be set as the bivalent group represented by these.

式Ｖｂにより表される構造単位：

またはこれらの組合せを含む。 In one embodiment, the polyetherimide is a structural unit represented by the formula Va:

Structural unit represented by the formula Vb:

Or a combination thereof.

  In one embodiment, R is p-phenylene, T is represented by the formula —O—Z—O—, the divalent bond of the —O—Z—O— group is in the 3,3 ′ position, and Z is The structural unit represented by Formula V, which is a divalent group represented by Formula XI, includes the structural unit represented by Formula Va.

  In one embodiment, R is m-phenylene, T is represented by the formula —O—Z—O—, the divalent bond of the —O—Z—O— group is in the 3,3 ′ position, and Z is The structural unit represented by Formula V, which is a divalent group represented by Formula XI, includes the structural unit represented by Formula Vb.

  In one embodiment, the polyetherimide comprises more than one structural unit, alternatively from about 10 to about 1,000 structural units, alternatively from about 10 to about 500 structural units, wherein the structural unit is represented by formula Va, formula It can be represented by Vb or a combination thereof.

In one embodiment, the polyetherimide sulfone comprises a structural unit represented by formula VI, and at least 50 mol% of the R groups can be independently represented by the formula of group IV and formula IVa, respectively, and Q and Q ^a can be —SO ₂ —, and the remaining R groups can each independently be p-phenylene, m-phenylene, or a combination thereof, and Y represents the formula —O—Z—. The divalent bond of the —O—Z—O— group can be in the 3,3 ′ position, and Z is a divalent group represented by the formula XI. It can be based.

  In one aspect, the polyetherimide sulfone can comprise repeating structural units derived from the polymerization of amines including diaminodiphenyl sulfone.

（式中、構造単位は、ｎ’回繰り返されることができ、ｎ’は、１超、あるいは約１０〜約１，０００、またはあるいは約１０〜約５００とすることができる）を含むことができる。 In one embodiment, the polyetherimide sulfone is a repeating structural unit represented by Formula VIa:

Wherein the structural unit can be repeated n ′ times, where n ′ can be greater than 1, or from about 10 to about 1,000, or alternatively from about 10 to about 500. it can.

In one embodiment, Y is represented by the formula —O—Z—O—, the divalent bond of the —O—Z—O— group is in the 3,3 ′ position, and Z is represented by the formula XI. R is a divalent group represented by formula IVa, Q ^a is —SO ₂ —, and each of the divalences of the divalent group R is para-to-SO ₂ —. The structural unit represented by formula VI in the position (4,4 ′ position) comprises the structural unit represented by formula VIa.

In one embodiment, the polyetherimide and / or polyetherimide sulfone is a substituted or unsubstituted aromatic primary such as, for example, substituted and unsubstituted anilines, substituted and unsubstituted naphthyl primary amines, and substituted and unsubstituted heteroarylamines. It can be end-capped with a monoamine and the substituents are C _6-12 aryl groups, halogenated C _6-12 aryl groups, C _1-12 alkyl groups, halogenated C _1-12 alkyl groups, sulfone groups, C _1-12. ester _{group, C 1 to 12} amide groups, _{halogens, C 1 to 12} alkyl ether _group, be selected from the group consisting of _{C 6 to 12} aryl keto group bonded to a _{C 6 to 12} aryl ether group, and an aromatic ring Can do. The attached functionality should not interfere with the function of the aromatic primary monoamine to control the molecular weight. Suitable examples of aromatic monoamines are described in more detail in U.S. Patent No. 6,057,028, which is incorporated herein by reference in its entirety. Non-limiting examples of aromatic monoamines suitable for use in the present disclosure include aniline, chloroaniline, perfluoromethylaniline, naphthylamine, and the like, or combinations thereof. In one embodiment, the aromatic monoamine comprises aniline.

  As recognized by those skilled in the art and with the aid of this disclosure, the amount of aromatic monoamine added during the preparation of polyetherimide and / or polyetherimide sulfone depends on the desired molecular weight and various other considerations. Can depend on. In one embodiment, the amount of aromatic monoamine present during the imide reaction is about 0 mol% to about 10 mol%, alternatively about 1 mol% to about 10 mol, relative to the total number of moles of aromatic diamine (eg, phenylenediamine). %, Alternatively about 2 mol% to about 10 mol%, alternatively about 5 mol% to about 9 mol%, or alternatively about 6 mol% to about 7 mol%. Further, as will be appreciated by those skilled in the art and with the aid of the present disclosure, the monofunctional reactant may be used at any time (eg, before or after initiating imidization (eg, aromatic diamines, aromatics). Dianhydride, solvent or combinations thereof), and in the presence or absence of an imidization catalyst. Furthermore, as will be appreciated by those skilled in the art and with the aid of the present disclosure, specific amounts can be determined by routine experimentation.

  In one embodiment, the relative amount of each reactant, the type and amount of catalyst, and the type and amount of aromatic primary monoamine, and the reaction conditions are from about 1.0 to about 1. per 1.0 amine group. 4 molar equivalents of anhydrous groups, alternatively about 1.0 to about 1.3 molar equivalents of anhydrous groups per 1.0 amine group, alternatively about 1.0 to about 1. About 1.0 to about 1.1 molar equivalents of anhydrous groups, or alternatively about 1.0 amine groups, about 1.0 to about 1 per 2 molar equivalents of anhydrous groups, or 1.0 amine groups It can be selected to provide a polyetherimide and / or polyetherimide sulfone having 0.002 molar equivalents of anhydrous groups.

  In one embodiment, the polyetherimide and / or polyetherimide sulfone can be further crosslinked. As recognized by those skilled in the art and with the aid of the present disclosure, methods for cross-linking polyetherimide and / or polyetherimide sulfone include, for example, cross-linking polyetherimide and / or polyetherimide sulfone. Any known polyetherimide and, for example, irradiating polyetherimide and / or polyetherimide sulfone (eg, an extruded film comprising polyetherimide and / or polyetherimide sulfone) And / or a method of crosslinking the polyetherimide sulfone. In one embodiment, the crosslinking of polyetherimide and / or polyetherimide sulfone can be achieved by UV irradiation at a wavelength greater than 280 nm and less than or equal to 400 nm.

  In one embodiment, the polyetherimide can be a branched polyetherimide, an unbranched polyetherimide, or a combination thereof. As recognized by those skilled in the art and with the help of the present disclosure, the degree of branching of the polyetherimide affects the strength properties of the polyetherimide, for example, the higher the content of branched polyetherimide, the higher the strength. Will improve.

  In one embodiment, the polyetherimide sulfone can be a branched polyetherimide sulfone, an unbranched polyetherimide sulfone, or a combination thereof. As recognized by those skilled in the art and with the help of the present disclosure, the degree of branching of polyetherimide sulfone affects the strength properties of polyetherimide sulfone, for example, high content of branched polyetherimide sulfone. The strength is improved.

  Polyetherimide and polyetherimide sulfone can be used alone or in combination. In some embodiments, the polymer composition for a capacitor film comprises a polyetherimide. In other embodiments, the polymer composition for a capacitor film comprises polyetherimide sulfone.

  In yet another embodiment, the capacitor film polymer composition comprises polyetherimide and polyetherimide sulfone. In such embodiments, the weight ratio of polyetherimide: polyetherimide sulfone is about 99: 1 to about 30:70, alternatively about 90:10 to about 40:60, or alternatively about 80:20 to about 60. : 40. As recognized by those skilled in the art and with the aid of the present disclosure, polyetherimide and polyetherimide sulfone form miscible polymer blends.

（式中、Ｎ_ｉは、分子量Ｍ_ｉの分子数である）に従って計算することができる。 In one embodiment, the polyetherimide and / or polyetherimide sulfone has a weight average molecular weight (Mw) of about 20,000 grams per mole (gw) as measured by gel permeation chromatography (GPC) using polystyrene standards. / Mol) or Daltons (Da) to about 400,000 Da, alternatively about 10,000 Da to about 400,000 Da, alternatively about 10,000 Da to about 200,000 Da, alternatively about 10,000 Da to about 80,000 Da, or alternatively about 50,000 Da to about 75,000 Da. In general, Mw is the formula 1:

Where N _i is the number of molecules of molecular weight M _i .

  In one embodiment, the polyetherimide and / or polyetherimide sulfone is less than about 100 ppm, alternatively less than about 50 ppm, or alternatively less than about 10 ppm, based on parts by weight of the polymer, as determined by proton nuclear magnetic resonance spectroscopy. It can have a benzylic content. The functional group of the benzylic proton can react at high temperature to accelerate the reaction that changes the molecular weight in the molten state. In another embodiment, the polyetherimide and / or polyetherimide sulfone may be free of, substantially free of, or essentially free of benzylic protons. Essentially free of benzylic protons means that the polyetherimide and / or polyetherimide sulfone product contains structural units derived from monomers and / or endcappers containing benzylic protons. It means having less than 5 mol%, alternatively less than about 3 mol%, or alternatively less than about 1 mol%. In one embodiment, the polyetherimide and / or polyetherimide sulfone is a polymer weight, as determined by proton nuclear magnetic resonance spectroscopy, structural units derived from monomers containing benzylic protons and / or end-capping agents. It can have 0 ppm or 0 mol% with respect to parts. In one embodiment, the polyetherimide and / or polyetherimide sulfone does not contain a benzylic proton.

  In one embodiment, the polyetherimide and / or polyetherimide sulfone is about 1,000 ppm or less, alternatively from about 0 ppm to about 1,000 ppm, based on parts by weight of the polyetherimide and / or polyetherimide sulfone, or Alternatively, it can have a bromine or chlorine content of about 0 ppm to about 500 ppm. The amount of bromine or chlorine can be determined by conventional chemical analysis such as atomic absorption. In one embodiment, the polyetherimide and / or polyetherimide sulfone is about 1,000 ppm or less, alternatively from about 0 ppm to about 1,000 ppm, based on parts by weight of the polyetherimide and / or polyetherimide sulfone, or Alternatively, it can have a total content of about 0 ppm to about 500 ppm plus bromine and chlorine.

  In one embodiment, the polyetherimide and / or polyetherimide sulfone can have low levels of organic reaction byproducts. For example, polyetherimide and / or polyetherimide sulfone may be 1,3-bis (N- (4-chlorophthalimide)) benzene, 1,1,2 based on parts by weight of polyetherimide and / or polyetherimide sulfone. Each having 3-bis (N-phthalimido) benzene, meta-phenylenediamine and bis (phthalimide) at a content of from about 0 ppm to about 500 ppm, alternatively from about 0 ppm to about 250 ppm, or alternatively from about 0 ppm to about 100 ppm; it can.

  In one embodiment, polyetherimide and / or polyetherimide sulfone is measured according to American Society for Testing and Materials (ASTM) D1238 at 340 ° C. to 370 ° C. under a load of 6.7 kilograms (kg). About 0.1 grams (g / min) to about 10 g / min, alternatively about 0.5 g / min to about 9.5 g / min, or alternatively about 1 g / min to about 9 g / min per minute. It can be characterized as an index.

  In one embodiment, the polyetherimide and / or polyetherimide sulfone is greater than or equal to about 0.2 deciliters per gram (dl / g), or about 0.2 dl / g, as measured in m-cresol at 25 ° C. An intrinsic viscosity of from about 0.8 dl / g, alternatively from about 0.3 dl / g to about 0.75 dl / g, or alternatively from about 0.35 dl / g to about 0.7 dl / g can be characterized. In general, fluid viscosity represents a measure by which a fluid resists gradual deformation due to shear or tensile stress. As used herein, the term “intrinsic viscosity” refers to the ratio of the specific viscosity of a polymer solution of known concentration to the concentration of solute (eg, the concentration of polymer in solution) extrapolated to zero concentration. As recognized by those skilled in the art and with the aid of this disclosure, the intrinsic viscosity (which is widely recognized as a standard measure of polymer properties) is directly proportional to the weight average molecular weight of the polymer. Intrinsic viscosity can be determined according to ASTM4603.

In one embodiment, the polyetherimide and / or polyether sulfone, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity and 5,000Sec ^-1 of 100 sec ^-1, less than about 11, or It may be characterized by less than about 10, alternatively less than about 9, or alternatively less than about 8.

  In one embodiment, the polyetherimide and / or polyetherimide sulfone is about 380,000 psi (2,618 MPa) or greater, alternatively about 400,000 psi (2,756 MPa) to about 620, as determined according to ASTM D638. 4,000 psi (4,272 MPa), alternatively from about 420,000 (2,893 MPa) to about 600,000 psi (4,134 MPa), or alternatively from about 425,000 psi (2,928 MPa) to about 580,000 psi (3,996 MPa). It can be characterized by having a tensile elastic modulus. In general, tensile modulus, also known as modulus or Young's modulus, is a measure of the stiffness of a material.

  In one embodiment, the polyetherimide and / or polyetherimide sulfone is about 150 ° C or higher, alternatively above about 160 ° C, alternatively above about 180 ° C, alternatively above about 200 ° C, alternatively from about 200 ° C to about 300 ° C, or alternatively It may be characterized by a glass transition temperature (Tg) of about 200 ° C. to about 290 ° C., or alternatively about 200 ° C. to about 280 ° C. In general, Tg refers to the temperature range in which a polymer transitions from a hard glassy material to a soft rubbery material. In one embodiment, the polyetherimide and / or polyetherimide sulfone can be characterized by one Tg (as opposed to multiple Tg values).

  In one embodiment, the polyetherimide comprises a commercially available polyetherimide, such as ULTEM resin, including, for example, ULTEM 1000 resin, ULTEM 1010 resin, ULTEM 9011 resin, or the like, or combinations thereof. ULTEM resins are a family of amorphous thermoplastic polyetherimide resins. ULTEM 1000 resin is a transparent amorphous polyetherimide plastic having a Tg of 217 ° C. ULTEM 1010 resin (e.g., ULTEM 1010K) is a transparent high flow PEI with a Tg of 217 ° C. ULTEM 9011 resin is a transparent, high flow PEI having a Tg of 217 ° C. Each of the above resins is available from SABIC Innovative Plastics. Polyetherimide resins are further described in ASTM D5205.

  In one embodiment, the polyetherimide sulfone comprises a commercially available polyetherimide sulfone, such as, for example, ULTEM XH6050 resin, which ULTEM XH6050 is a clear, flowable polyetherimide sulfone homopolymer having a Tg of 247 ° C. And available from SABIC Innovative Plastics.

  In one embodiment, the polyetherimide and / or polyetherimide sulfone is within the capacitor film polymer composition, from about 0.1 weight percent (wt%) to about the total weight of the capacitor film polymer composition. About 99.9%, alternatively about 1% to about 99%, alternatively about 10% to about 90%, alternatively about 25% to about 75%, alternatively about 40% to about 60% Or about 45% to about 55%, alternatively about 50% to about 99.9%, alternatively about 50% to about 99%, alternatively about 50% to about 90%, or about It can be present in an amount of 50% to about 75% by weight. In one embodiment, the polymer composition for the capacitor film comprises about 50% by weight polyetherimide and / or polyetherimide sulfone.

  In one embodiment, the polyetherimide comprises about 15% by weight of a polyetherimide other than a polyetherimide comprising units derived from polymerization of an amine comprising m-phenylenediamine, p-phenylenediamine, etc., or combinations thereof. Less than, or less than about 10%, or alternatively less than about 5% by weight.

  In one embodiment, the polymer composition for a capacitor film comprises polycarbonate. The polycarbonate can be a homopolymer or a copolymer. In some embodiments, the polycarbonate can be a polycarbonate copolymer; a copolymer of polycarbonate and siloxane; a copolymer of polycarbonate and polycarbonate-ester, or the like, or a combination thereof. In one embodiment, the polycarbonate comprises poly (carbonate-arylate ester), the poly (carbonate-arylate ester) comprising bisphenol carbonate repeat units and arylate ester repeat units that are different from each other.

（式中、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルキル基、Ｃ_１〜１２アルケニル基、Ｃ_３〜８シクロアルキル基またはＣ_１〜１２アルコキシ基とすることができ、ｐおよびｑは、それぞれ独立して、０〜４とすることができ、Ｘ^ａは、２つのアリーレン基の間の架橋基とすることができ、
Ｘ^ａは、単結合、−Ｏ−、−Ｓ−、−Ｓ（Ｏ）−、−Ｓ（Ｏ）_２−、−Ｃ（Ｏ）−、式−Ｃ（Ｒ^ｃ）（Ｒ^ｄ）−であるＣ_１〜１１アルキリデン基とすることができ、Ｒ^ｃおよびＲ^ｄは、それぞれ独立して、水素、Ｃ_１〜１０アルキル基、または式−Ｃ（＝Ｒ^ｅ）−の基であり、Ｒ^ｅは、二価Ｃ_１〜１０炭化水素基とすることができる）により表されるビスフェノールカーボネート単位である、繰り返し単位を有する化合物を指す。本開示における使用に好適なＸ^ａ基の非限定例は、メチレン、エチリデン、ネオペンチリデン、イソプロピリデンなど、またはこれらの組合せを含む。一実施形態では、架橋基Ｘ^ａ、および各Ｃ_６アリーレン基のカーボネート酸素原子は、Ｃ_６アリーレン基に対して、互いに、オルト、メタまたはパラに配置することができる。一実施形態では、架橋基Ｘ^ａ、および各Ｃ_６アリーレン基のカーボネート酸素原子は、Ｃ_６アリーレン基に対して、互いにパラに配置することができる。 As used herein, the terms “polycarbonate” and “polycarbonate polymer” have the formula XII:

(Wherein, R ^a and R ^b can each independently be a C _1-12 alkyl group, a C _1-12 alkenyl group, a C _3-8 cycloalkyl group, or a C _1-12 alkoxy group, p and q can each independently be 0 to 4; X ^a can be a bridging group between two arylene groups;
X ^a is a single bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, or a formula —C (R ^c ) (R ^d ) —. A C _1-11 alkylidene group, wherein R ^c and R ^d are each independently hydrogen, a C _1-10 alkyl group, or a group of formula —C (═R ^e ) — ^e can be a divalent _C1-10 hydrocarbon group) and is a bisphenol carbonate unit represented by the compound having a repeating unit. Non-limiting examples of suitable X ^a group for use in the present disclosure include methylene, ethylidene, neopentylidene, and isopropylidene, or a combination thereof. In one embodiment, the bridging group X ^a and the carbonate oxygen atom of each C ₆ arylene group can be placed ortho, meta, or para with respect to the C ₆ arylene group. In one embodiment, the bridging group X ^a and the carbonate oxygen atom of each C ₆ arylene group can be located para to each other relative to the C ₆ arylene group.

In one embodiment, R ^a and R ^b can each independently be a C _1-3 alkyl group, p and q can each independently be 0-1 and X ^a Is a single bond, —O—, —S (O) —, —S (O) ₂ —, —C (O) —, C ₁ to C ₁ represented by the formula —C (R ^c ) (R ^d ) — _{. 9} alkylidene groups, wherein R ^c and R ^d are each independently hydrogen, a C _1-8 alkyl group, or a group represented by the formula —C (═R ^e ) —, and R ^e Can be a divalent C _1-9 hydrocarbon group. In another embodiment, R ^a and R ^b can each independently be a methyl group, p and q can each independently be 0 to 1, and X ^a is a single bond , A C _1-7 alkylidene group represented by the formula —C (R ^c ) (R ^d ) —, wherein R ^c and R ^d are each independently hydrogen or a C _1-6 alkyl group; can do. In one embodiment, p and q are each 1, R ^a and R ^b are each independently a C _1-3 alkyl group (eg, methyl), and R ^a and R ^b are each ring Above can be arranged meta to oxygen.

In one embodiment, the bisphenol carbonate unit represented by formula XII can be derived from bisphenol A, p and q can both be 0, and X ^a can be isopropylidene. .

（式中、Ｒ^１は、架橋部分とすることができる）から生成することができる。一般に、式ＸＩＩにより表されるビスフェノールカーボネート単位は、式ＸＩＶにより表される、対応するビスフェノール化合物：

（式中、Ｒ^ａおよびＲ^ｂ、ｐおよびｑおよびＸ^ａは、式ＸＩＩにより表されるビスフェノールカーボネート単位に関して、本明細書に既に記載されている）から生成することができる。このようなＲ^ａおよびＲ^ｂ、ｐおよびｑ、ならびにＸ^ａの説明の態様および／または実施形態のいずれも、非限定的に利用して、式ＸＩＶのＲ^ａおよびＲ^ｂ、ｐおよびｑ、ならびにＸ^ａを記載することができる。 In one embodiment, the polycarbonate unit is represented by formula XIII, a dihydroxy compound:

(Wherein R ¹ can be a bridging moiety). In general, the bisphenol carbonate unit represented by formula XII is represented by the corresponding bisphenol compound represented by formula XIV:

Wherein R ^a and R ^b , p and q and X ^a have already been described herein with respect to the bisphenol carbonate unit represented by formula XII. Any of the described aspects and / or embodiments of R ^a and R ^b , p and q, and X ^a can be utilized, without limitation, for R ^a and R ^{b of} formula XIV, p and q, as well as to describe the X ^a.

  Non-limiting examples of bisphenol compounds suitable for use in the present disclosure to produce bisphenol carbonate units represented by Formula XII include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,2 -Bis (4-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 1,2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2, 2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-t- Til-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3 -Methoxy-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, or the like Includes combinations.

  In one embodiment, bisphenol compounds suitable for producing bisphenol carbonate units represented by Formula XII are 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane. 2,2-bis (4-hydroxyphenyl) propane ("bisphenol A" or "BPA"), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-2-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane or the like, or combinations thereof.

（式中、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルケニル基、Ｃ_３〜８シクロアルキル基またはＣ_１〜１２アルコキシとすることができ、ｐおよびｑは、それぞれ独立して、０〜４の整数とすることができ、Ｘ^ｂは、ポリカーボネートコポリマー中の架橋基Ｘ^ａと同じではない、Ｃ_２〜３２架橋炭化水素基とすることができる）により表される、ビスフェノールカーボネート単位とすることができる。一実施形態では、架橋基Ｘ^ｂ、および各Ｃ_６アリーレン基のカーボネート酸素原子は、Ｃ_６アリーレン基に対して、互いに、オルト、メタまたはパラに配置することができる。一実施形態では、架橋基Ｘ^ｂ、および各Ｃ_６アリーレン基のカーボネート酸素原子は、Ｃ_６アリーレン基に対して、互いにパラに配置することができる。 In one embodiment, the polycarbonate polymer can be a copolymer further comprising a second type of carbonate repeat unit (as opposed to and different from the bisphenol carbonate repeat unit represented by Formula XII). . The second type of carbonate repeating unit can also be a bisphenol carbonate unit (wherein the bisphenol carbonate unit has different conditions than the bisphenol carbonate unit represented by Formula XII) or an arylate ester unit. In one embodiment, the second type of carbonate repeat unit is of formula XV:

Wherein R ^a and R ^b can each independently be a C _1-12 alkenyl group, a C _3-8 cycloalkyl group, or a C _1-12 alkoxy, and p and q are each independently Te, can be an integer of 0 to 4, X ^b are the same though not the bridging group X ^a in the polycarbonate copolymer is represented by may be a C _{2 to 32} crosslinkable hydrocarbon group), bisphenol It can be a carbonate unit. In one embodiment, the bridging group X ^b and the carbonate oxygen atom of each C ₆ arylene group can be placed ortho, meta or para with respect to the C ₆ arylene group. In one embodiment, the bridging group X ^b and the carbonate oxygen atom of each C ₆ arylene group can be placed para to each other with respect to the C ₆ arylene group.

In one embodiment, X ^b is represented by a substituted or unsubstituted C _3-18 cycloalkylidene group, a substituted or unsubstituted C _3-18 cycloalkylene group, the formula —C (R ^c ) (R ^d ) —. Or substituted or unsubstituted C _12-25 alkylidene groups, wherein R ^c and R ^d are each independently hydrogen, C _1-24 alkyl group, C _4-12 cycloalkyl group, C _{6- A 12} aryl group, a C _7-12 aryl alkylene group, a C _1-12 heteroalkyl group or a cyclic C _7-12 heteroarylalkyl group, or a group represented by the formula —C (═R ^e ) —. And R ^e can be a divalent C _12-31 hydrocarbon group. Non-limiting examples of ^Xb groups suitable for use in the present disclosure include cyclohexylmethylidene, 1,1-ethene, 2- [2.2.1] -bicycloheptylidene, cyclohexylidene, cyclopentylidene, cyclo Dodecylidene, adamantylidene, etc., or combinations thereof.

In one embodiment, ^{X b} is the formula ^{-C (R c) (R d} ) - can be a substituted or unsubstituted _{C 5 to 32} alkylidene group represented by, ^{R c} and ^{R d,} respectively Independently represented by hydrogen, a C _4-12 cycloalkyl group, a C _6-12 aryl group, a C _7-12 aryl alkylene group, a C _1-12 heteroalkyl group, a formula —C (═R ^e ) —. R ^e may be a divalent C _12-31 hydrocarbyl group, a substituted or unsubstituted C _5-18 cycloalkylidene group, a substituted or unsubstituted C _5-18 cycloalkylene group , A substituted or unsubstituted C _3-18 heterocycloalkylidene group, or a group represented by the formula -B ¹ -GB ^2- , wherein B ¹ and B ² are the same or different C _{1- 6} Can be alkylene groups, G _may be a _{C 3 to 12} cycloalkylidene group or a _{C 6 to 16} arylene group.

（式中、Ｒ^ｒ、Ｒ^ｐ、Ｒ^ｑおよびＲ^ｔは、それぞれ独立して、水素、酸素またはＣ_１〜１２有機基とすることができ、Ｉは、直接結合、炭素または二価の酸素、硫黄または−Ｎ（Ｚ）−とすることができ、Ｚは、水素、ハロゲン，ヒドロキシ、Ｃ_１〜１２アルキル基、Ｃ_１〜１２アルコキシ基またはＣ_１〜１２アシル基とすることができ、ｈは、０〜２とすることができ、ｊは、１または２とすることができ、ｉは、０または１の整数とすることができ、ｋは、０〜３の整数であり、Ｒ^ｒ、Ｒ^ｐ、Ｒ^ｑおよびＲ^ｔのうちの少なくとも２つは、一緒になって、縮合脂環式環、芳香族環または複素芳香族環である）により表される、置換Ｃ_３〜１８ヘテロシクロアルキリデン基とすることができる。当業者により認識されている通り、および本開示の一助により、縮合環が芳香族である場合、式ＸＶａにおいて表されている環は、この環が縮合している、炭素−炭素不飽和連結基を有する。ｋが１であり、ｉが０である場合、式ＸＶａにおいて表される環は、４個の炭素原子を含有し、ｋが２である場合、式ＸＶａにおいて表される環は、５個の炭素原子を含有し、ｋが３である場合、式ＸＶａにおいて表される環は、６個の炭素原子を含有する。一実施形態では、Ｒ^ｒ、Ｒ^ｐ、Ｒ^ｑおよびＲ^ｔのうちの隣接する２つの基（例えば、Ｒ^ｑおよびＲ^ｔが一緒になって）は、芳香族基を形成する。別の実施形態では、Ｒ^ｑおよびＲ^ｔは、一緒になって、第１の芳香族基を形成し、Ｒ^ｒおよびＲ^ｐは一緒になって、第２の芳香族基を形成する。Ｒ^ｑおよびＲ^ｔが、一緒になって、芳香族基を形成する場合、Ｒ^ｐは、二重結合をしている酸素原子、すなわちケトンとすることができる。 In one embodiment, ^Xb is of the formula XVa:

Wherein R ^r , R ^p , R ^q and R ^t can each independently be hydrogen, oxygen or a C _1-12 organic group, where I is a direct bond, carbon or divalent oxygen , Sulfur or —N (Z) —, where Z can be hydrogen, halogen, hydroxy, a C _1-12 alkyl group, a C _1-12 alkoxy group or a C _1-12 acyl group, h can be 0-2, j can be 1 or 2, i can be 0 or an integer of 1, k is an integer of 0-3, R at least two of ^{r 1} , R ^p , R ^q and R ^{t taken} together are a fused alicyclic, aromatic or heteroaromatic ring), substituted C _3-18 It can be a heterocycloalkylidene group. As recognized by those skilled in the art and with the assistance of the present disclosure, when the fused ring is aromatic, the ring represented in Formula XVa is a carbon-carbon unsaturated linking group to which the ring is fused. Have When k is 1 and i is 0, the ring represented by formula XVa contains 4 carbon atoms, and when k is 2, the ring represented by formula XVa is 5 When containing carbon atoms and k is 3, the ring represented by formula XVa contains 6 carbon atoms. In one embodiment, two adjacent groups of R ^r , R ^p , R ^q and R ^t (eg, R ^q and R ^{t taken} together) form an aromatic group. In another embodiment, R ^q and R ^t are taken together to form a first aromatic group, and R ^r and R ^p are taken together to form a second aromatic group. When R ^q and R ^t together form an aromatic group, R ^p can be a double-bonded oxygen atom, ie a ketone.

（式中、Ｒ^ａ、Ｒ^ｂ、ｐおよびｑは、式ＸＶにより表されるビスフェノールカーボネート単位に関して、本明細書に既に記載されている）により表される、フタルイミドカーボネート単位を含むことができる。このようなＲ^ａ、Ｒ^ｂ、ｐおよびｑの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＸＶｂにより表されるフタルイミドカーボネート単位を記載することができる。各Ｒ^３は、それぞれ独立して、Ｃ_１〜６アルキル基とすることができ、ｊは、０〜４であり、Ｒ^４は、水素、Ｃ_１〜６アルキル基、または１〜５つのＣ_１〜６アルキル基により場合により置換されているフェニル基とすることができる。一実施形態では、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜３アルキル基とすることができる。 In one embodiment, the second type of carbonate repeat unit comprising a bisphenol carbonate unit has the formula XVb:

(Wherein R ^a , R ^b , p, and q are already described herein with respect to the bisphenol carbonate unit represented by formula XV). Any of the described aspects and / or embodiments of R ^a , R ^b , p and q can be utilized in a non-limiting manner to describe a phthalimido carbonate unit represented by the formula XVb. Each R ³ can independently be a C _1-6 alkyl group, j is 0-4, and R ⁴ is hydrogen, a C _1-6 alkyl group, or 1-5 C It can be a phenyl group optionally substituted by _1-6 alkyl groups. In one embodiment, R ^a and R ^b can each independently be a C _1-3 alkyl group.

（式中、Ｒ^５は、水素、最大で５つのＣ_１〜６アルキル基により場合により置換されているフェニル、またはＣ_１−４アルキル基とすることができる）により表すことができる。一実施形態では、Ｒ^５は、水素、フェニルまたはメチルとすることができる。一実施形態では、Ｒ^５がフェニルである、式ＸＶｃにより表されるカーボネート単位は、２−フェニル−３，３’−ビス（４−ヒドロキシフェニル）フタルイミジン（Ｎ−フェニルフェノールフタレインビスフェノール、または「ＰＰＰ−ＢＰ」としても知られている）（３，３−ビス（４−ヒドロキシフェニル）−２−フェニルイソインドリン−１−オンとしても知られている）から誘導することができる。 In one embodiment, the phthalimidocarbonate unit has the formula XVc:

Wherein R ⁵ can be hydrogen, phenyl optionally substituted with up to five C _1-6 alkyl groups, or a C _1-4 alkyl group. In one embodiment, R ⁵ can be hydrogen, phenyl or methyl. In one embodiment, the carbonate unit represented by formula XVc, wherein R ⁵ is phenyl, is 2-phenyl-3,3′-bis (4-hydroxyphenyl) phthalimidine (N-phenylphenolphthalein bisphenol, or “ (Also known as “PPP-BP”) (also known as 3,3-bis (4-hydroxyphenyl) -2-phenylisoindoline-1-one).

（式中、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルキル基とすることができ、ｐおよびｑは、それぞれ独立して、０〜４とすることができ、Ｒ^ｉは、Ｃ_１〜１２アルキル基、１〜４つのＣ_１〜１０アルキル基により場合により置換されているフェニル基、または１〜５つのＣ_１〜１０アルキル基により場合により置換されているベンジル基とすることができる）により表される、イサチンカーボネート単位を含むことができる。一実施形態では、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、メチルとすることができ、ｐおよびｑは、それぞれ独立して、０または１であり、Ｒ^ｉは、Ｃ_１〜４アルキル基またはフェニルとすることができる。 In other embodiments, the bisphenol carbonate repeating unit is of formula XVd and XVe:

Wherein R ^a and R ^b can each independently be a C _1-12 alkyl group, p and q can each independently be 0-4, and R ⁱ is , A C _1-12 alkyl group, a phenyl group optionally substituted with _{1 to} 4 C _1-10 alkyl groups, or a benzyl group optionally substituted with _{1 to} 5 C _1-10 alkyl groups. Isatin carbonate units represented by: In one embodiment, R ^a and R ^b can each independently be methyl, p and q are each independently 0 or 1, and R ⁱ is a C _1-4 alkyl group. Or it can be phenyl.

（式中、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルキル基とすることができ、Ｒ^ｇは、Ｃ_１〜１２アルキル基とすることができ、ｐおよびｑは、それぞれ独立して、０〜４とすることができ、ｔは、０〜１０とすることができる）により表される、シクロヘキシリデン架橋されているアルキル置換ビスフェノールを含む。一実施形態では、Ｒ^ａおよびＲ^ｂのそれぞれのうちの少なくとも１つは、シクロヘキシリデン架橋基に対してメタに配置することができる。一実施形態では、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜４アルキル基とすることができ、Ｒ^ｇは、Ｃ_１〜４アルキル基とすることができ、ｐおよびｑは、それぞれ独立して、０または１であり、ｔは０〜５とすることができる。別の実施形態では、Ｒ^ａ、Ｒ^ｂおよびＲ^ｇは、それぞれ独立して、メチルとすることができ、ｒおよびｓは、それぞれ独立して、０または１とすることができ、ｔは、０または３とすることができる。別の実施形態では、Ｒ^ａ、Ｒ^ｂおよびＲ^ｇは、それぞれ独立して、メチルとすることができ、ｒおよびｓは、それぞれ独立して、０または１とすることができ、ｔは、０とすることができる。 Non-limiting examples of bisphenol carbonate units represented by Formula XV where X ^b is a substituted or unsubstituted C _3-18 cycloalkylidene group include Formula XVf:

Wherein R ^a and R ^b can each independently be a C _1-12 alkyl group, R ^g can be a C _1-12 alkyl group, and p and q are each Independently, it can be 0-4, t can be 0-10) and includes cyclohexylidene-bridged alkyl-substituted bisphenols. In one embodiment, at least one of each of R ^a and R ^b can be placed meta to the cyclohexylidene bridging group. In one embodiment, R ^a and R ^b can each independently be a C _1-4 alkyl group, R ^g can be a C _1-4 alkyl group, and p and q are Each is independently 0 or 1, and t can be 0-5. In another embodiment, R ^a , R ^b and R ^g can each independently be methyl, r and s can each independently be 0 or 1, and t is It can be 0 or 3. In another embodiment, R ^a , R ^b and R ^g can each independently be methyl, r and s can each independently be 0 or 1, and t is It can be set to zero.

（式中、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルキル基とすることができ、ｐおよびｑは、それぞれ独立して、１〜４とすることができる）を含む、置換または無置換のＣ_３〜１８シクロアルキリデン基とすることができる。一実施形態では、Ｒ^ａおよびＲ^ｂのそれぞれのうちの少なくとも１つは、シクロアルキリデン架橋基に対してメタに配置することができる。一実施形態では、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜３アルキル基とすることができ、ｐおよびｑは、それぞれ独立して、０または１である。一実施形態では、Ｒ^ａおよびＲ^ｂは、それぞれ、メチル基とすることができ、ｐおよびｑは、それぞれ独立して、０または１とすることができ、ｐおよびｑが１である場合、メチル基は、シクロアルキリデン架橋基にたいして対してメタに配置している。 In one embodiment, the bisphenol carbonate unit represented by Formula XV is an adamantyl unit represented by Formula XVg and a fluorenyl unit represented by Formula XVh:

Wherein R ^a and R ^b can each independently be a C _1-12 alkyl group, and p and q can each independently be 1-4. It can be a substituted or unsubstituted C _3-18 cycloalkylidene group. In one embodiment, at least one of each of R ^a and R ^b can be placed meta to the cycloalkylidene bridging group. In one embodiment, R ^a and R ^b can each independently be a C _1-3 alkyl group, and p and q are each independently 0 or 1. In one embodiment, R ^a and R ^b can each be a methyl group, p and q can each independently be 0 or 1, and when p and q are 1, The methyl group is located in the meta relative to the cycloalkylidene bridging group.

  In one embodiment, a carbonate containing units represented by the formulas XVa, XVb, XVc, XVd, XVe, XVf, XVg and XVh produces a polycarbonate having a high glass transition temperature (Tg) and a high heat distortion temperature. Can be useful to do.

（式中、Ｒ^ａ、Ｒ^ｂ、ｐ、ｑおよびＸ^ｂは、式ＸＶにより表されるビスフェノールカーボネート単位に関して、本明細書に既に記載されている）から一般に生成することができる。このようなＲ^ａ、Ｒ^ｂ、ｐ、ｑおよびＸ^ｂの説明の態様および／または実施形態のいずれも、非限定的に利用して、式ＸＶＩにより表されるビスフェノール化合物を記載することができる。 In one embodiment, the bisphenol carbonate unit represented by formula XV is a corresponding bisphenol compound represented by formula XVI:

(Wherein R ^a , R ^b , p, q and X ^b are already described herein with respect to the bisphenol carbonate unit represented by formula XV). Any of the described aspects and / or embodiments of R ^a , R ^b , p, q and X ^b can be utilized in a non-limiting manner to describe a bisphenol compound represented by Formula XVI. .

  Non-limiting examples of bisphenol compounds suitable for use in the present disclosure represented by Formula XVI include bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 1, 6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspiro (bis) indane (“spirobiindanebisphenol”), 2,6-dihydroxy Dibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxatin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 2,7-dihydroxycarbazole, 2,6-dihydride Xithianthrene 3,3-bis (4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPP-BP), 1,1-bis (4-hydroxy-3- Methylphenyl) cyclohexane (DMBPC) and the like, or combinations thereof.

  In one embodiment, the molar ratio of the bisphenol carbonate unit represented by formula XII to the bisphenol carbonate unit represented by formula XV is that of the polycarbonate composition including considerations such as Tg, impact strength, ductility, and fluidity. Depending on the desired properties, about 99: 1 to about 1:99, alternatively about 90:10 to about 10:90, alternatively about 80:20 to about 20:80, alternatively about 70:30 to about 30:70, Alternatively, it can range from about 60:40 to about 40:60. When the bisphenol carbonate unit represented by Formula XII is derived from bisphenol A units, the bisphenol A units are generally present in an amount of about 50 mol% to 99 mol%, based on the total number of moles of bisphenol units in the polycarbonate copolymer. be able to. Further, when the bisphenol carbonate unit represented by formula XII is derived from bisphenol A, the bisphenol unit represented by formula XV and the bisphenol unit represented by formula XII and the formula XV are derived from PPP-BP. Can be from about 99: 1 to about 50:50, or from about 90:10 to about 55:45.

（式中、Ｒ^ｈはそれぞれ、独立して、ハロゲン原子、Ｃ_１〜１０アルキル基などのＣ_１〜１０ヒドロカルビル基、ハロゲン置換Ｃ_１〜１０アルキル基、Ｃ_６〜１０アリール基またはハロゲン置換Ｃ_６〜１０アリール基とすることができ、ｎは、０〜４とすることができる）により表される、モノアリールジヒドロキシ化合物を含む。このような実施形態では、ハロゲンは、臭素となり得る。一実施形態では、式ＸＶＩＩにより表されるモノアリールジヒドロキシ化合物は、ハロゲンを含まない。 In one embodiment, the polycarbonate polymer disclosed herein is in a relatively small amount, for example, less than about 20 mol%, less than about 10 mol%, or about relative to the total number of moles of carbonate units in the polycarbonate copolymer. Other carbonate units can be included in an amount of less than 5 mol%. In one embodiment, the other carbonate unit is, for example, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspiro (bis) indane. ("Spirobiindane bisphenol"), 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxatin, 2,7-dihydroxy-9,10-dimethylphenazine, 3 Aliphatic having 1 to 32 carbon atoms, such as, 6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 2,7-dihydroxycarbazole and 2,6-dihydroxythianthrene, or combinations thereof, or It can be derived from an aromatic dihydroxy compound. In one embodiment, the aromatic dihydroxy compound has the formula XVII:

(Wherein, each ^{R h,} independently, a halogen _{atom, C 1 to 10} hydrocarbyl group such as _{C 1 to 10} alkyl group, a halogen-substituted _{C 1 to 10} alkyl _{group, C 6 to 10} aryl group or a halogen-substituted C _6-10 aryl groups, and n can be 0-4). In such embodiments, the halogen can be bromine. In one embodiment, the monoaryldihydroxy compound represented by Formula XVII does not contain a halogen.

  Non-limiting examples of monoaryl dihydroxy compounds represented by Formula XVII suitable for use in the present disclosure include resorcinol, substituted resorcinol compounds, 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butyl Resorcinol, 5-t-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromoresorcinol; Catechol; hydroquinone; substituted hydroquinone, 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-t-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 2, 3, 5 , 6-Tetramethylhy Including such, or a combination thereof; hydroquinone, 2,3,5,6 -t- butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone.

（式中、Ｒ^ｈはそれぞれ独立して、ハロゲンまたはＣ_１〜１０炭化水素基とすることができ、ｎは、０〜４とすることができる）により表されるモノアリールカーボネート単位を含む。一実施形態では、Ｒ^ｈはそれぞれ、独立して、Ｃ_１〜３アルキル基とすることができ、ｎは０〜１とすることができる。一実施形態では、Ｒ^ｈはそれぞれ、独立して、Ｃ_１〜３アルキル基とすることができ、ｎは０とすることができる。別の実施形態では、式ＸＩＩによりおよび式ＸＶにより表されるビスフェノールカーボネート単位以外のカーボネート単位は、ポリカーボネートコポリマー中に存在する。 In one embodiment, the polycarbonate copolymer is a bisphenol carbonate unit represented by Formula XII and Formula XV, and a carbonate unit derived from less than about 10 mol% of a monoaryl dihydroxy compound represented by Formula XVII, ie, Formula XVIIa :

(Wherein R ^h each independently can be a halogen or a C _1-10 hydrocarbon group, and n can be 0 to 4). In one embodiment, each R ^h can independently be a C _1-3 alkyl group and n can be 0-1. In one embodiment, each R ^h can independently be a C _1-3 alkyl group and n can be 0. In another embodiment, carbonate units other than the bisphenol carbonate units represented by Formula XII and by Formula XV are present in the polycarbonate copolymer.

（式中、Ａｒ^１は、少なくとも１つの芳香族基、例えば、フェニル、ナフタレン、アントラセンなど、またはこれらの組合せを含有するＣ_６〜３２ヒドロカルビル基とすることができる）により表されるアリレートエステル繰り返し単位を含む。一実施形態では、Ａｒ^１は、式ＸＩＩによりおよび式ＸＶにより表されるビスフェノールカーボネート単位、式ＸＶＩＩにより表されるモノアリールジヒドロキシ化合物、またはこれらの組合せに関連して上で記載されている芳香族ビスフェノールから誘導することができる。一実施形態では、式ＸＶＩＩＩにより表されるアリレートエステル単位は、イソフタル酸、テレフタル酸またはこれらの組合せ（本明細書において「フタル酸」と称される）と、本明細書において既に記載されている芳香族ビスフェノール、すなわち式ＸＶＩＩにより表されるモノアリールジヒドロキシ化合物のいずれか、またはこれらの組合せとの反応により誘導することができる。一実施形態では、イソフタレートとテレフタレートとのモル比は、約１：９９〜約９９：１、あるいは約８０：２０〜約２０：８０、またはあるいは約６０：４０〜約４０：６０とすることができる。 In one embodiment, the poly (carbonate-arylate ester) is a bisphenol carbonate repeating unit represented by Formula XII and Formula XVIII:

Wherein Ar ¹ can be a C _6-32 hydrocarbyl group containing at least one aromatic group, such as phenyl, naphthalene, anthracene, etc., or combinations thereof. Includes units. In one embodiment, Ar ¹ is an aromatic as described above in connection with a bisphenol carbonate unit represented by formula XII and a monoaryldihydroxy compound represented by formula XVII, or a combination thereof. It can be derived from bisphenol. In one embodiment, the arylate ester unit represented by Formula XVIII is already described herein as isophthalic acid, terephthalic acid, or a combination thereof (referred to herein as “phthalic acid”). It can be derived by reaction with an aromatic bisphenol, ie any of the monoaryl dihydroxy compounds represented by formula XVII, or combinations thereof. In one embodiment, the molar ratio of isophthalate to terephthalate is about 1:99 to about 99: 1, alternatively about 80:20 to about 20:80, or alternatively about 60:40 to about 40:60. Can do.

（式中、Ｒ^１およびＡｒ^１は、それぞれ、式ＸＩＩにより表されるビスフェノールカーボネート単位および式ＸＶＩＩＩにより表されるアリレートエステル単位について、本明細書において既に記載されている）とすることができる。このようなＲ^１およびＡｒ^１の説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＸＩＸにより表されるコポリマーを記載することができる。 In one embodiment, the poly (carbonate-arylate ester) comprising a bisphenol carbonate unit represented by Formula XII and an arylate ester unit represented by Formula XVIII is an alternating or block copolymer represented by Formula XIX:

Wherein R ¹ and Ar ¹ are already described herein for the bisphenol carbonate unit represented by formula XII and the arylate ester unit represented by formula XVIII, respectively. Any such illustrative aspect and / or embodiment of R ¹ and Ar ¹ can be utilized in a non-limiting manner to describe a copolymer represented by Formula XIX.

  In general, poly (carbonate-arylate esters) are block copolymers containing carbonate blocks and ester blocks. In one embodiment, the weight ratio of total ester units to total carbonate units in the copolymer (eg, poly (carbonate-arylate ester)) depends on the desired properties of the polycarbonate composition, such as from about 99: 1 to about 1:99, alternatively about 95: 5 to about 5:95, alternatively about 90:10 to about 10:90, or alternatively about 90:10 to about 50:50. The molar ratio of isophthalate to terephthalate in the ester units in the copolymer can also be, for example, from about 0: 100 to about 100: 0, or from about 92: 8 to about 8 :, depending on the desired properties of the polycarbonate composition. 92, or alternatively about 98: 2 to about 45:55. In one embodiment, the weight ratio of total ester units to total carbonate can be about 99: 1 to about 40:60, or alternatively about 90:10 to about 50:40, and the isophthalate to terephthalate The molar ratio can be from about 99: 1 to about 40:50, or alternatively from about 98: 2 to about 45:55, depending on the desired properties of the polycarbonate composition.

  In one embodiment, the polycarbonate copolymer provides additional carbonate units derived from the dihydroxy compound used to form the arylate ester unit represented by Formula XVIII relative to the total number of moles of units in the polycarbonate copolymer. Less than about 20 mol%, alternatively less than about 10 mol%, or alternatively less than about 5 mol%. In one embodiment, the polycarbonate copolymer comprises additional arylate ester units derived from the reaction of phthalic acid with the monoaryldihydroxy compound represented by Formula XVII used to form carbonate units. In an amount of less than about 20 mol%, alternatively less than about 10 mol%, alternatively less than about 5 mol%, or alternatively less than about 1 mol%, relative to the total number of moles of units therein. In one embodiment, the combination of such additional carbonate units and such additional arylate ester units is less than about 20 mol% in the polycarbonate copolymer relative to the total number of moles of units in the polycarbonate copolymer, or about It can be present in an amount of less than 10 mol%, alternatively less than about 5 mol%, or alternatively less than about 1 mol%.

（式中、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルキル基、Ｃ_１〜１２アルケニル基、Ｃ_３〜８シクロアルキル基またはＣ_１〜１２アルコキシ基とすることができ、ｐおよびｑは、それぞれ独立して、０〜４とすることができ、Ｘ^ａは、２つのアリーレン基の間の架橋基とすることができ、Ｘ^ａは、単結合、−Ｏ−、−Ｓ−、−Ｓ（Ｏ）−、−Ｓ（Ｏ）_２−、−Ｃ（Ｏ）−、式−Ｃ（Ｒ^ｃ）（Ｒ^ｄ）−により表されるＣ_１〜１１アルキリデン基とすることができ、Ｒ^ｃおよびＲ^ｄは、それぞれ独立して、水素、Ｃ_１〜１０アルキル基、または式−Ｃ（＝Ｒ^ｅ）−により表される基とすることができ、Ｒ^ｅは、二価Ｃ_１〜１０炭化水素基とすることができる）により表すことができる。一実施形態では、ｐおよびｑは、それぞれ独立して、０または１とすることができ、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、各環上の酸素に対してメタに配置しているＣ_１〜３アルキル基とすることができ、Ｘ^ａは、式−Ｃ（Ｒ^ｃ）（Ｒ_ｄ）−により表されるアルキリデンとすることができ、Ｒ^ｃおよびＲ^ｄは、それぞれ、Ｃ_１〜６アルキル基とすることができる。一実施形態では、ｐおよびｑは、それぞれ独立して、０または１とすることができ、Ｒ^ａおよびＲ^ｂは、それぞれ、各環上の酸素に対してメタに配置されているメチル基とすることができ、Ｘ^ａは、式−Ｃ（Ｒ^ｃ）（Ｒ^ｄ）−により表されるアルキリデンとすることができ、Ｒ^ｃおよびＲ^ｄは、それぞれ、Ｃ_１〜６アルキル基とすることができる。一実施形態では、ビスフェノールは、ビスフェノールＡとすることができ、ｐおよびｑは、どちらも０であり、Ｘ^ａはイソプロピリデンである。 In one embodiment, the poly (carbonate-arylate ester) comprises poly (carbonate) -co- (bisphenol arylate) comprising a bisphenol carbonate unit represented by Formula XII (eg, bisphenol A carbonate unit) and a bisphenol arylate ester repeat unit. Ester). In such embodiments, the bisphenol arylate unit can include phthalic acid residues and bisphenols, such as, for example, bisphenols represented by Formula XIII. In one embodiment, the bisphenol arylate ester unit is of formula XVIIIa:

(Wherein, R ^a and R ^b can each independently be a C _1-12 alkyl group, a C _1-12 alkenyl group, a C _3-8 cycloalkyl group, or a C _1-12 alkoxy group, p and q can each independently be 0 to 4, X ^a can be a bridging group between two arylene groups, and X ^a is a single bond, —O—, — It shall be _C1-11 alkylidene group represented by S-, -S (O)-, -S (O) _2- , -C (O)-, and the formula -C ( ^Rc ) ( ^Rd )- R ^c and R ^d can each independently be hydrogen, a C _1-10 alkyl group, or a group represented by the formula —C (═R ^e ) —, where R ^e is Valent C _1-10 hydrocarbon group). In one embodiment, p and q can each independently be 0 or 1, and R ^a and R ^b are each independently placed meta to the oxygen on each ring. A C _1-3 alkyl group, X ^a can be an alkylidene represented by the formula —C (R ^c ) (R _d ) —, wherein R ^c and R ^d are each C ₁ it can be a ₆ alkyl group. In one embodiment, p and q can each independently be 0 or 1, and R ^a and R ^b are each a methyl group located meta to the oxygen on each ring and X ^a can be an alkylidene represented by the formula —C (R ^c ) (R ^d ) —, where R ^c and R ^d are each a C _1-6 alkyl group Can do. In one embodiment, the bisphenol can be bisphenol A, p and q are both a 0, X ^a is isopropylidene.

（式中、ｙおよびｘは、それぞれ、アリレート−ビスフェノールＡエステル単位およびビスフェノールＡカーボネート単位を表す）により表される、ポリ（ビスフェノールＡカーボネート）−ｃｏ−（ビスフェノールＡ−フタレート−エステル）とすることができる。一般に、単位は、ブロックとして存在する。一実施形態では、コポリマー中でのエステル単位ｙの重量％とカーボネート単位ｘの重量％との比は、約５０：５０〜約９９：１、あるいは約５５：４５〜約９０：１０、またはあるいは約７５：２５〜約９５：５の範囲とすることができる。エステル単位が、イソフタレートとテレフタレートとのモル比が約４５：５５〜約５５：４５を有する、約３５重量％〜約４５重量％のカーボネート単位および約５５重量％〜約６５重量％のエステル単位を含む、式ＸＩＸａにより表されるコポリマーは、ポリ（カーボネート−エステル）（ＰＣＥ）と呼ばれることが多い。エステル単位が、イソフタレートとテレフタレートとのモル比が約９８：２〜約８８：１２を有する、約１５重量％〜約２５重量％のカーボネート単位および約７５重量％〜約８５重量％のエステル単位を含む、式ＸＩＸａにより表されるコポリマーは、ポリ（フタレート−カーボネート）（ＰＰＣ）と呼ばれることが多い。 In one embodiment, the poly (carbonate-arylate ester) has the formula XIXa:

(Wherein y and x represent an arylate-bisphenol A ester unit and a bisphenol A carbonate unit, respectively) and are represented by poly (bisphenol A carbonate) -co- (bisphenol A-phthalate-ester) Can do. In general, units exist as blocks. In one embodiment, the ratio of weight percent ester units y to weight percent carbonate units x in the copolymer is about 50:50 to about 99: 1, alternatively about 55:45 to about 90:10, or alternatively It can range from about 75:25 to about 95: 5. From about 35 wt% to about 45 wt% carbonate units and from about 55 wt% to about 65 wt% ester units, wherein the ester units have a molar ratio of isophthalate to terephthalate of about 45:55 to about 55:45 Copolymers represented by Formula XIXa, including are often referred to as poly (carbonate-esters) (PCE). From about 15 wt% to about 25 wt% carbonate units and from about 75 wt% to about 85 wt% ester units, wherein the ester units have a molar ratio of isophthalate to terephthalate of about 98: 2 to about 88:12 Copolymers represented by Formula XIXa, including, are often referred to as poly (phthalate-carbonate) (PPC).

（式中、Ｒ^ｈはそれぞれ、独立して、ハロゲン原子、Ｃ_１〜１０アルキル基などのＣ_１〜１０ヒドロカルビル基、ハロゲン置換Ｃ_１〜１０アルキル基、Ｃ_６〜１０アリール基またはハロゲン置換Ｃ_６〜１０アリール基とすることができ、ｎは、０〜４とすることができる）により表されるモノアリールアリレートエステル繰り返し単位を含有するポリ（カーボネート）−ｃｏ−（モノアリールアリレートエステル）を含む。一実施形態では、Ｒ^ｈはそれぞれ、独立して、Ｃ_１〜４アルキル基とすることができ、ｎは０〜３、あるいは０〜１、またはあるいは０とすることができる。一実施形態では、ポリ（カーボネート）−ｃｏ−（モノアリールアリレートエステル）コポリマーは、式ＸＩＸｂ：

（式中、ｘ：ｍのモル比は、約９９：１〜約１：９９、あるいは約８０：２０〜約２０：８０、またはあるいは約６０：４０〜約４０：６０とすることができ、Ｒ^１は、式ＸＩＩにより表されるビスフェノールカーボネート単位に関して、本明細書に既に記載されており、Ｒ^ｈおよびｎは、式ＸＶＩＩＩｂにより表されるモノアリールアリレートエステル単位に関して、本明細書に既に記載されている）によって表すことができる。このようなＲ^１、Ｒ^ｈおよびｎの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＸＩＸｂにより表されるポリ（カーボネート）−ｃｏ−（モノアリールアリレートエステル）コポリマーを記載することができる。 In another embodiment, the poly (carbonate-arylate ester) is a carbonate unit represented by Formula XII and Formula XVIIIb:

(Wherein, each ^{R h,} independently, a halogen _{atom, C 1 to 10} hydrocarbyl group such as _{C 1 to 10} alkyl group, a halogen-substituted _{C 1 to 10} alkyl _{group, C 6 to 10} aryl group or a halogen-substituted C A poly (carbonate) -co- (monoaryl arylate ester) containing monoaryl arylate ester repeating units represented by: _6-10 aryl groups, n can be 0-4) Including. In one embodiment, each R ^h can independently be a C _1-4 alkyl group and n can be 0-3, alternatively 0-1, or alternatively 0. In one embodiment, the poly (carbonate) -co- (monoaryl arylate ester) copolymer has the formula XIXb:

Wherein the x: m molar ratio can be from about 99: 1 to about 1:99, alternatively from about 80:20 to about 20:80, alternatively from about 60:40 to about 40:60, R ¹ has already been described herein with respect to the bisphenol carbonate unit represented by Formula XII, and R ^h and n have already been described herein with respect to the monoaryl arylate ester unit represented by Formula XVIIIb. Can be represented by). Any such described aspect and / or embodiment of R ¹ , R ^h and n can be utilized in a non-limiting manner to represent poly (carbonate) -co- (monoaryl arylate ester) represented by Formula XIXb Copolymers can be described.

（式中、ｍは、約４〜約１００、あるいは約４〜約９０、あるいは約５〜約７０、あるいは約５〜約５０、またはあるいは約１０〜約３０とすることができる）により表されるイソフタレート−テレフタレート−レゾルシノール（「ＩＴＲ」）エステル単位をもたらすことができる。一実施形態では、ＩＴＲエステル単位は、ポリカーボネートコポリマー中、該コポリマー中のエステル単位の総モル数に対して、約９５ｍｏｌ％以上、あるいは約９９ｍｏｌ％超、またはあるいは約９９．５ｍｏｌ％超の量で存在することができる。（イソフタレート−テレフタレート−レゾルシノール）−カーボネートコポリマー（「ＩＴＲ−ＰＣ」コポリマー）は、例えば靭性、透明度、熱流特性および耐候性などの、多数の望ましい特徴を有することができる。ＩＴＲ−ＰＣコポリマーは、界面重合技法を使用して、商業規模で容易に製造することができ、この技法により、ＩＴＲ−ＰＣコポリマーの合成において、人工的可撓性および組成物特異性を可能にすることができる。 In one embodiment, the monoaryl-arylate ester unit represented by Formula XVIIIb is derived from the reaction of a combination of isophthalic acid and terephthalic diacid (or a derivative thereof) with resorcinol (or a reactive derivative thereof) Formula XVIIIc:

Wherein m can be about 4 to about 100, alternatively about 4 to about 90, alternatively about 5 to about 70, alternatively about 5 to about 50, or alternatively about 10 to about 30. Isophthalate-terephthalate-resorcinol ("ITR") ester units. In one embodiment, the ITR ester units are present in the polycarbonate copolymer in an amount greater than or equal to about 95 mol%, alternatively greater than about 99 mol%, or alternatively greater than about 99.5 mol%, relative to the total number of moles of ester units in the copolymer. Can exist. (Isophthalate-terephthalate-resorcinol) -carbonate copolymers ("ITR-PC" copolymers) can have a number of desirable characteristics such as toughness, clarity, heat flow properties, and weather resistance. ITR-PC copolymers can be easily manufactured on a commercial scale using interfacial polymerization techniques, which allow artificial flexibility and composition specificity in the synthesis of ITR-PC copolymers. can do.

（式中、ｍは、約４〜約１００、あるいは約４〜約９０、あるいは約５〜約７０、あるいは約５〜約５０、またはあるいは約１０〜約３０とすることができ、ｘ：ｍのモル比は、約９９：１〜約１：９９、またはあるいは約９０：１０〜約１０：９０とすることができる）により表される、ポリ（ビスフェノールＡカーボネート）−ｃｏ−（イソフタレート−テレフタレート−レゾルシノールエステル）とすることができる。一実施形態では、ＩＴＲエステル単位は、ポリ（カーボネート−アリレートエステル）コポリマー中に、該コポリマー中のエステル単位の総モル数に対して、約９５ｍｏｌ％以上、あるいは約９９ｍｏｌ％超、またはあるいは約９９．５ｍｏｌ％超の量で存在することができる。一実施形態では、追加のカーボネート単位、追加のエステル単位、またはこれらの組合せは、コポリマー中に、該コポリマー中の単位の総モル数に対して、約１ｍｏｌ％〜約２０ｍｏｌ％の量で存在することができる。このような実施形態では、追加のカーボネート単位は、式ＸＸ：

により表されるレゾルシノールカーボネート単位および式ＸＶＩＩＩａにより表されるビスフェノールエステル単位を含むことができ、式中、Ｒ^ｈは、それぞれ独立して、Ｃ_１〜１０炭化水素基とすることができ、ｎは０〜４とすることができる、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルキル基とすることができ、ｐおよびｑは、それぞれ独立して、０〜４の整数とすることができ、Ｘ^ａは、単結合、−Ｏ−、−Ｓ−、−Ｓ（Ｏ）−、−Ｓ（Ｏ）_２−、−Ｃ（Ｏ）−、または式−Ｃ（Ｒ^ｃ）（Ｒ^ｄ）−であるＣ_１〜１３アルキリデン基とすることができ、Ｒ^ｃおよびＲ^ｄは、それぞれ独立して、水素、Ｃ_１〜１２アルキル基、または式−Ｃ（＝Ｒ^ｅ）−により表される基とすることができ、Ｒ^ｅは、二価Ｃ_１〜１２炭化水素基とすることができる。一実施形態では、ビスフェノールエステル単位は、式ＸＸＩ：

により表される、ビスフェノールＡフタレートエステル単位とすることができる。 In one embodiment, the poly (carbonate) -co- (monoaryl arylate ester) has the formula XIXc:

Wherein m can be about 4 to about 100, alternatively about 4 to about 90, alternatively about 5 to about 70, alternatively about 5 to about 50, alternatively about 10 to about 30, and x: m Can be from about 99: 1 to about 1:99, or alternatively from about 90:10 to about 10:90), poly (bisphenol A carbonate) -co- (isophthalate- Terephthalate-resorcinol ester). In one embodiment, the ITR ester units are present in the poly (carbonate-arylate ester) copolymer in an amount greater than or equal to about 95 mol%, alternatively greater than about 99 mol%, or alternatively about 99 mol, relative to the total moles of ester units in the copolymer. It can be present in an amount greater than 5 mol%. In one embodiment, the additional carbonate units, additional ester units, or combinations thereof are present in the copolymer in an amount from about 1 mol% to about 20 mol%, based on the total number of moles of units in the copolymer. be able to. In such embodiments, the additional carbonate unit is of formula XX:

And a resorcinol carbonate unit represented by formula XVIIIa and a bisphenol ester unit represented by formula XVIIIa, wherein R ^h can independently be a C _1-10 hydrocarbon group, and n is R ^a and R ^b , which can be 0 to 4, can be each independently a C _1-12 alkyl group, and p and q are each independently an integer of 0 to 4. X ^a can be ^a single bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, or a formula —C (R ^c ) ( R ^d ) — can be a C _1-13 alkylidene group, wherein R ^c and R ^d are each independently hydrogen, a C _1-12 alkyl group, or a formula —C (═R ^e ) —. can be a group represented, ^{R e} is a divalent _{C. 1 to} It can be ₂ hydrocarbon groups. In one embodiment, the bisphenol ester unit has the formula XXI:

It can be set as the bisphenol A phthalate ester unit represented by these.

  In one embodiment, the poly (bisphenol A carbonate) -co- (isophthalate-terephthalate-resorcinol ester) represented by Formula XIXc is about 1 mol% to about 20 mol% bisphenol A carbonate units, about 60 mol% to about 99 mol. % Isophthalic acid-terephthalic acid-resorcinol ester units, and optionally from about 1 mol% to about 20 mol% resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate ester units, or combinations thereof. In another embodiment, the poly (bisphenol A carbonate) -co- (isophthalate-terephthalate-resorcinol ester) represented by Formula XIXc is about 70 mol% to about 90 mol% bisphenol A carbonate units, about 10 mol% to about 30 mol% isophthalic acid-terephthalic acid-resorcinol ester units, and optionally from about 1 mol% to about 60 mol% resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A ester units, or combinations thereof.

により表されるポリシロキサン単位とすることができ、式中、Ｒはそれぞれ独立して、Ｃ_１〜１３一価ヒドロカルビル基とすることができる。一実施形態では、Ｒはそれぞれ独立して、Ｃ_１〜１３アルキル基、Ｃ_１〜１３アルコキシ基、Ｃ_２〜１３アルケニル基、Ｃ_２〜１３アルケニルオキシ基、Ｃ_３〜６シクロアルキル基、Ｃ_３〜６シクロアルコキシ基、Ｃ_６〜１４アリール基、Ｃ_６〜１０アリールオキシ基、Ｃ_７〜１３アリールアルキル基、Ｃ_７〜１３アリールアルコキシ基、Ｃ_７〜１３アルキルアリール基、またはＣ_７〜１３アルキルアリールオキシ基とすることができる。このような実施形態では、Ｒ基のそれぞれは、独立して、フッ素、塩素、臭素もしくはヨウ素、またはこれらの組合せにより、完全にまたは部分的にハロゲン化され得る。一実施形態では、Ｒ基はハロゲンを含有しない。当業者により認識されている通り、および本開示の一助により、例示的なＲ基の組合せは、同一のコポリマー中に使用することができる。一実施形態では、ポリシロキサンは、最小限の炭化水素含有率を有するＲ基を含み、例えば、Ｒはメチル基とすることができる。 In another embodiment, the poly (carbonate-arylate ester) copolymer is a siloxane unit (also known as a “diorganosiloxane unit”), such as poly (bisphenol-A carbonate) -co-poly (isophthalate-terephthalate). -Resorcinol ester) -co-poly (siloxane) copolymer. For convenience, poly (bisphenol-A carbonate) -co-poly (isophthalate-terephthalate-resorcinol ester) -co-poly (siloxane) is referred to herein as an “ITR-PC-siloxane” copolymer. In general, poly (carbonate-siloxane) copolymers can also be referred to as “PC-siloxane” or “PC-Si” copolymers. In one embodiment, the ITR-PC-siloxane copolymer is a carbonate unit represented by Formula XII derived from a bisphenol represented by Formula XIV (eg, bisphenol-A), a monoaryl arylate ester represented by Formula XVIIIb Contains units and siloxane units. In one embodiment, the ITR-PC-siloxane copolymer comprises bisphenol-A carbonate units, an ITR ester unit represented by Formula XVIIIc, and a siloxane unit, wherein the siloxane unit is of Formula XXII:

In which R is independently a _C1-13 monovalent hydrocarbyl group. In one embodiment, R is _{independently, C 1 to 13} alkyl _{groups, C 1 to 13} alkoxy _{groups, C 2 to 13} alkenyl _{groups, C 2 to 13} alkenyloxy _{groups, C 3 to 6} cycloalkyl groups, C _3-6 cycloalkoxy _{group, C having 6 to 14} aryl _{group, C 6 to 10} aryloxy _{group, C 7 to 13} arylalkyl _{group, C 7 to 13} arylalkoxy _{group, C 7 to 13} alkylaryl group, or _{C. 7 to,} It can be a ₁₃ alkylaryloxy group. In such embodiments, each of the R groups can independently be fully or partially halogenated with fluorine, chlorine, bromine or iodine, or combinations thereof. In one embodiment, the R group does not contain a halogen. As recognized by those skilled in the art and with the aid of this disclosure, exemplary R group combinations can be used in the same copolymer. In one embodiment, the polysiloxane includes R groups having a minimum hydrocarbon content, for example, R can be a methyl group.

により表される構造単位とすることができ、式中、ＥおよびＲは、式ＸＸＩＩにより表されるポリシロキサン単位に関して、本明細書に既に記載されており、Ｒはそれぞれ、独立して、同一または異なることができ、Ａｒはそれぞれ、独立して、同一または異なることができ、Ａｒはそれぞれ、独立して、芳香族基を含有する置換または無置換のＣ_６〜３０化合物とすることができ、結合は、芳香族基に直接、結合することができる。このような先のＥおよびＲの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＸＸＩＩａにより表されるポリシロキサン構造単位を記載することができる。一実施形態では、式ＸＸＩＩａにおけるＡｒ基は、Ｃ_６〜３０ジヒドロキシ芳香族化合物（例えば、本明細書に既に記載されているビスフェノール化合物）、式ＸＶＩＩにより表されるモノアリールジヒドロキシ化合物、またはこれらの組合せから誘導することができる。本開示における使用に好適なＣ_６〜３０ジヒドロキシ芳香族化合物の非限定例には、レゾルシノール（すなわち、１，３−ジヒドロキシベンゼン）、４−メチル−１，３−ジヒドロキシベンゼン、５−メチル−１，３−ジヒドロキシベンゼン、４，６−ジメチル−１，３−ジヒドロキシベンゼン、１，４−ジヒドロキシベンゼン、１，１−ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）オクタン、１，１−ビス（４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）ｎ−ブタン、２，２−ビス（４−ヒドロキシ−１−メチルフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、ビス（４−ヒドロキシフェニルスルフィド）、１，１−ビス（４−ヒドロキシ−ｔ−ブチルフェニル）プロパンなど、またはこれらの組合せが含まれる。一実施形態では、Ｃ_６〜３０ジヒドロキシ芳香族化合物は、無置換とすることができる。一実施形態では、Ｃ_６〜３０ジヒドロキシ芳香族化合物は、アルキル、アルコキシまたはアルキレン置換基などの非芳香族ヒドロカルビル置換基を含有しない。 The average value of E in Formula XXII takes into account the type and relative amount of each component in the polycarbonate composition, whether the polymer is a linear, branched or graft copolymer, the above desired properties of the composition, etc. Depending on the point, it can vary widely. In one embodiment, E is from about 2 to about 500, alternatively from about 2 to about 200, alternatively from about 5 to about 120, alternatively from about 10 to about 100, alternatively from about 10 to about 80, alternatively from about 2 to about 30, or Alternatively, it can have an average value of about 30 to about 80. In one embodiment, E can have an average value of about 16 to about 50, alternatively about 20 to about 45, or alternatively about 25 to about 45. In another embodiment, E may have an average value of about 4 to about 50, alternatively about 4 to about 15, alternatively about 5 to about 15, alternatively about 6 to about 15, or alternatively about 7 to about 10. In one embodiment, the polysiloxane unit can have the formula XXIIa:

Wherein E and R have already been described herein with respect to the polysiloxane unit represented by formula XXII, and each R is independently the same Or each can independently be the same or different and each Ar can independently be a substituted or unsubstituted _C6-30 compound containing an aromatic group. The bond can be directly bonded to the aromatic group. Any of the foregoing description aspects and / or embodiments of E and R can be utilized in a non-limiting manner to describe the polysiloxane structural unit represented by Formula XXIIa. In one embodiment, the Ar group in formula XXIIa is a C _6-30 dihydroxy aromatic compound (eg, a bisphenol compound already described herein), a monoaryl dihydroxy compound represented by formula XVII, or these Can be derived from a combination. Non-limiting examples of C _6-30 dihydroxy aromatic compounds suitable for use in the present disclosure include resorcinol (ie 1,3-dihydroxybenzene), 4-methyl-1,3-dihydroxybenzene, 5-methyl-1 , 3-dihydroxybenzene, 4,6-dimethyl-1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxy) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-1-methyl) Ruphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl sulfide), 1,1-bis (4-hydroxy-t-butylphenyl) propane, or the like, or combinations thereof It is. In one embodiment, the C _6-30 dihydroxy aromatic compound can be unsubstituted. In one embodiment, the C _6-30 dihydroxy aromatic compound does not contain non-aromatic hydrocarbyl substituents such as alkyl, alkoxy or alkylene substituents.

により表すことができる。 In one embodiment where Ar is derived from resorcinol, the polysiloxane unit is of the formula XXIIa-1:

Can be represented by

により表すことができる。 In another embodiment where Ar is derived from bisphenol A, the polysiloxane unit is of the formula XXIIa-2:

Can be represented by

  In one embodiment, the polysiloxane unit can comprise a polysiloxane unit represented by Formula XXIIa-1, a polysiloxane unit represented by Formula XXIIa-2, or a combination thereof, where E is, for example, E It can have an average value already described herein, such as having an average value of about 2 to about 200.

により表されるポリジオルガノシロキサン単位を含むことができ、式中、Ｒ^２はそれぞれ、独立して、Ｃ_１〜３０ヒドロカルビレン基またはＣ_２〜１４ヒドロカルビレン基（例えば、二価Ｃ_１〜３０アルキレン基またはＣ_７〜３０アリーレン−アルキレン基など）とすることができ、ＲおよびＥは、式ＸＸＩＩにより表されるポリシロキサン単位に関して本明細書に既に記載されている。このような先のＥおよびＲの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＸＸＩＩｂにより表されるポリジオルガノシロキサン単位を記載することができる。本明細書における本開示の目的として、「Ｅ−１」とは「Ｅマイナス１」を指し、具体的に式に関して、ポリシロキサン単位中のＳｉ単位の数はＥに保存されることが意図され、ここで、１個のＳｉは角括弧の繰り返しの外側に置かれている。［（Ｅ−１）＋１（角括弧の外側のＳｉ）］＝Ｅ In yet another embodiment, the polysiloxane unit is of the formula XXIIb:

In which each R ² is independently a C _1-30 hydrocarbylene group or a C _2-14 hydrocarbylene group (eg, divalent C _{1). ˜30} alkylene groups or C _7-30 arylene-alkylene groups, etc.), and R and E have already been described herein with respect to the polysiloxane units represented by formula XXII. Any of the foregoing description aspects and / or embodiments of E and R can be utilized non-limitingly to describe polydiorganosiloxane units represented by Formula XXIIb. For purposes of this disclosure herein, “E-1” refers to “E minus 1”, and specifically with respect to the formula, the number of Si units in the polysiloxane unit is intended to be stored in E. Here, one Si is placed outside the repetition of the square brackets. [(E-1) +1 (Si outside square brackets)] = E

によって表すことができ、式中、Ｒ^３はそれぞれ独立して、二価Ｃ_２〜８脂肪族基とすることができ、ＲおよびＥは、式ＸＸＩＩにより表されるポリシロキサン単位に関して、本明細書に既に記載されている。このような先のＥおよびＲの説明の態様および／または実施形態のいずれも、非限定的に利用されて、式ＸＸＩＩｂ−１により表されるポリジオルガノシロキサン単位を記載することができる。式ＸＸＩＩｂ−１におけるＭはそれぞれ、同一または異なることができ、ハロゲン、シアノ基、ニトロ基、Ｃ_１〜８アルキルチオ基、Ｃ_１〜８アルキル基、Ｃ_１〜８アルコキシ基、Ｃ_２〜８アルケニル基、Ｃ_２〜８アルケニルオキシ基、Ｃ_３〜８シクロアルキル基、Ｃ_３〜８シクロアルコキシ基、Ｃ_６〜１０アリール基、Ｃ_６〜１０アリールオキシ基、Ｃ_７〜１２アリールアルキル基、Ｃ_７〜１２アリールアルコキシ基、Ｃ_７〜１２アルキルアリール基またはＣ_７〜１２アルキルアリールオキシ基とすることができ、ｎはそれぞれ独立して、０、１、２、３または４とすることができる。一実施形態では、Ｍは、ブロモまたはクロロ、アルキル基（例えば、メチル、エチル、プロピル）、アルコキシ基（例えば、メトキシ、エトキシ、プロポキシ）またはアリール基（例えば、フェニル、クロロフェニル、トリル）とすることができ、Ｒ^３は、ジメチレン、トリメチレンまたはテトラメチレン基とすることができ、Ｒは、Ｃ_１〜８アルキル基、ハロアルキル基（例えば、トリフルオロプロピル）、シアノアルキル基またはアリール基（例えば、フェニル、クロロフェニル、トリル）とすることができる。別の実施形態では、Ｒはメチル、メチルとトリフルオロプロピルとの組合せ、またはメチルとフェニルとの組合せとすることができる。さらに別の実施形態では、Ｍはメトキシとすることができ、ｎは０または１とすることができ、Ｒ^３は、二価Ｃ_１〜３脂肪族基とすることができ、Ｒはメチルとすることができる。 In one embodiment of Formula XXIIb, where R ² is a C _7-30 arylene-alkylene group, the polydiorganosiloxane unit is of Formula XXIIb-1:

Wherein R ³ can each independently be a divalent C _2-8 aliphatic group, and R and E are as defined herein for a polysiloxane unit represented by formula XXII: Already described in the book. Any of the foregoing description aspects and / or embodiments of E and R can be utilized in a non-limiting manner to describe the polydiorganosiloxane unit represented by Formula XXIIb-1. Each M in formula XXIIb-1 can be the same or different and is halogen, cyano group, nitro group, C _1-8 alkylthio group, C _1-8 alkyl group, C _1-8 alkoxy group, C _2-8 alkenyl. Group, C _2-8 alkenyloxy group, C _3-8 cycloalkyl group, C _3-8 cycloalkoxy group, C _6-10 aryl group, C _6-10 aryloxy group, C _7-12 arylalkyl group, C _{It can be a 7-12} arylalkoxy group, a _C7-12 alkylaryl group or a _C7-12 alkylaryloxy group, and n can be independently 0, 1, 2, 3 or 4. . In one embodiment, M is bromo or chloro, an alkyl group (eg, methyl, ethyl, propyl), an alkoxy group (eg, methoxy, ethoxy, propoxy) or an aryl group (eg, phenyl, chlorophenyl, tolyl). R ³ can be a dimethylene, trimethylene or tetramethylene group, and R can be a C _1-8 alkyl group, a haloalkyl group (eg, trifluoropropyl), a cyanoalkyl group or an aryl group (eg, phenyl , Chlorophenyl, tolyl). In another embodiment, R can be methyl, a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In yet another embodiment, M can be methoxy, n can be 0 or 1, R ³ can be a divalent C _1-3 aliphatic group, R is methyl and can do.

により表されるオイゲノールによりキャップされているポリシロキサン単位とすることができ、式中、Ｅは、本明細書に既に記載されている平均値、あるいは約２〜約２００、あるいは約２〜約１００、あるいは約２〜約９０、あるいは約２〜約８０、あるいは約２〜約３０、あるいは約２０〜約１００、またはあるいは約３０〜約８０を有することができる。 In one embodiment, the polysiloxane unit has the formula XXIIb-2:

In which E is the average value already described herein, alternatively from about 2 to about 200, alternatively from about 2 to about 100. Or about 2 to about 90, alternatively about 2 to about 80, alternatively about 2 to about 30, alternatively about 20 to about 100, alternatively about 30 to about 80.

を含むことができ、式中、Ｅは、本明細書に既に記載されている平均値、あるいは約２〜約２００、あるいは約２〜約１００、あるいは約２〜約９０、あるいは約２〜約８０、あるいは約２〜約３０、あるいは約２０〜１００、またはあるいは約３０〜約８０を有することができる。 In another embodiment, the polysiloxane unit is a polysiloxane unit represented by formula XXIIb-3 or formula XXIIb-4:

Wherein E is the average value already described herein, alternatively from about 2 to about 200, alternatively from about 2 to about 100, alternatively from about 2 to about 90, alternatively from about 2 to about 80, alternatively about 2 to about 30, alternatively about 20 to 100, or alternatively about 30 to about 80.

  As recognized by those skilled in the art and with the aid of this disclosure, the relative amount of polysiloxane units represented by Formula XXII in the ITR-PC-siloxane copolymer can be determined, for example, impact resistance, smoke density, heat dissipation and melting. Depends on the desired properties of the copolymer composition (eg, thermoplastic composition), such as viscosity. In one embodiment, the poly (carbonate-arylate ester) has an average value of E that can provide good impact and / or transparency properties, and in the copolymer composition, the desired weight percent of siloxane. You can choose to yield units. In one embodiment, the poly (carbonate-arylate ester) contains siloxane units from about 0.3 wt% to about 30 wt%, alternatively about 0.5 wt%, based on the total weight of the polymer in the copolymer composition. Up to about 25% by weight, or alternatively from about 0.5% to about 15% by weight, wherein the siloxane units are covalently bonded in the polymer backbone of the poly (carbonate-arylate ester). Can be provided by siloxane units.

  In one embodiment, the ITR-PC-siloxane copolymer is represented by about 1 mol% to about 40 mol%, or alternatively about 1 mol% to about 20 mol% of bisphenol-A carbonate units, about 50 mol% to about 95 mol% of formula XVIIIc. And an amount of polysiloxane units represented by Formula XXIIb effective to provide about 0.1 wt% to about 10 wt% siloxane units, wherein mol% is in the copolymer Based on the total number of moles of units, weight percent is based on the total weight of the copolymer.

  In one embodiment, the ITR-PC-siloxane copolymer is represented by about 1 mol% to about 40 mol%, or alternatively about 1 mol% to about 20 mol% of bisphenol-A carbonate units, about 50 mol% to about 95 mol% of formula XVIIIc. An amount of Formula XXIIb-1, Formula XXIIb-2, Formula XXIIb-3, Formula XXIIb-4 in an amount effective to provide about 0.1 wt% to about 10 wt% siloxane units Polysiloxane units or combinations thereof, where mol% is based on the total number of moles of units in the copolymer and weight% is based on the total weight of the copolymer. In some embodiments, the polysiloxane unit can comprise a polysiloxane unit represented by Formula XXIIb-1. In other embodiments, the polysiloxane units can include polysiloxane units represented by Formula XXIIb-2, Formula XXIIb-3, Formula XXIIb-4, or combinations thereof.

  In one embodiment, the ITR-PC-siloxane copolymer is represented by about 1 mol% to about 40 mol%, or alternatively about 1 mol% to about 20 mol% of bisphenol-A carbonate units, about 50 mol% to about 95 mol% of formula XVIIIc. An ITR ester unit and an amount of polysiloxane unit represented by Formula XXIIb-2 effective to provide about 0.1 wt% to about 10 wt% siloxane unit, wherein mol% is a copolymer Based on the total number of moles of units in, weight percent is based on the total weight of the copolymer.

  In one embodiment, the ITR-PC-siloxane copolymer comprises about 1 mol% to about 20 mol% bisphenol-A carbonate units, about 60 mol% to about 90 mol% ITR ester units represented by Formula XVIIIc, and about 0.1 An amount of polysiloxane units represented by Formula XXIIb-2, Formula XXIIb-3, Formula XXIIb-4, or a combination thereof, effective to provide from wt% to about 10 wt% siloxane units, % Is based on the total number of moles of units in the copolymer, and weight% is based on the total weight of the copolymer.

  In one embodiment, the ITR-PC-siloxane copolymer comprises about 1 mol% to about 20 mol% bisphenol-A carbonate units, about 60 mol% to about 90 mol% ITR ester units represented by Formula XVIIIc, and about 0.1 mol%. An effective amount of polysiloxane units represented by Formula XXIIb-2 can be included to provide from about 10% to about 10% by weight siloxane units, where mol% is based on the total number of moles of units in the copolymer. % By weight is based on the total weight of the copolymer.

  In one embodiment, the PC can be manufactured by methods such as interfacial polymerization and melt polymerization. Although the reaction conditions for interfacial polymerization can vary, exemplary methods generally involve dissolving or dispersing the dihydric phenol reactant in aqueous caustic soda or caustic potash, and mixing the resulting mixture with a water-miscible solvent. Adding the reactants to the carbonate precursor in the presence of a catalyst, such as a tertiary amine and / or a phase transfer catalyst, under the control of pH conditions, eg, at about pH 8 to about pH 12, Includes steps. Non-limiting examples of water-immiscible solvents suitable for use in the present disclosure include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene, etc., or combinations thereof.

  Non-limiting examples of carbonate precursors suitable for use in the present disclosure include carbonyl halides, carbonyl bromides, carbonyl chlorides, haloformates, bishaloformates of dihydric phenols, bischloroformates of bisphenol A, hydroquinones Bischloroformates, glycol bishaloformates, ethylene glycol bishaloformates, neopentyl glycol bishaloformates, polyethylene glycol bishaloformates, or combinations thereof. In one embodiment, the interfacial polymerization reaction to form the carbonate linking group can use phosgene as the carbonate precursor and is referred to as a phosgenation reaction.

  In one embodiment, the tertiary amine is trimethylamine, tributylamine, alicyclic tertiary amine, N, N-diethyl-cyclohexylamine, aromatic tertiary amine, N, N-dimethylaniline, etc., or combinations thereof Can be included.

In one embodiment, the phase transfer catalyst can comprise a catalyst of formula (R ³ ) ₄ Q ⁺ X, each R ³ can be the same or different, and each R ³ is independently C It can be a _1-10 alkyl group, Q can be a nitrogen or phosphorus atom, and X can be a halogen atom, a _C1-8 alkoxy group or a _C6-18 aryloxy group. Non-limiting examples of phase transfer catalysts suitable for use in the present disclosure include [CH ₃ (CH ₂ ) ₃ ] ₄ NX, [CH ₃ (CH ₂ ) ₃ ] ₄ PX, [CH ₃ (CH ₂ ) ₅ ] ₄ NX, [CH ₃ (CH ₂ ) ₆ ] ₄ NX, [CH ₃ (CH ₂ ) ₄ ] ₄ NX, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NX and CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NX is included, and X can be a Cl ⁻ , Br ⁻ , C _1-8 alkoxy group or a C _6-18 aryloxy group. In one embodiment, the phase transfer catalyst is an effective amount of about 0.1 wt% to about 10 wt%, or alternatively about 0.5 wt% to about 2 wt%, based on the weight of bisphenol in the phosgenation mixture. Can be used in

に従って計算することができ、式中、Ｎ_ｉは、分子量Ｍ_ｉの分子数である。 In an alternative embodiment, a melting process can be used to make the polycarbonate. Melt polymerization can be carried out as a batch process or as a continuous process. In any case, the melt polymerization conditions used may include two or more separate reaction stages, such as a first reaction stage in which the starting dihydroxy aromatic compound and diaryl carbonate are converted to polycarbonate oligomers, and a first A second reaction stage can be included in which the polycarbonate oligomer formed in the reaction stage is converted to a high molecular weight polycarbonate. Such “staged” polymerization reaction conditions are such that the feed monomer is oligomerized in a first reaction vessel and the polycarbonate oligomer formed in the first reaction vessel is continuously connected to one or more downstream reactors. It is particularly suitable for use in a continuous polymerization system in which the polycarbonate oligomer is converted to high molecular weight polycarbonate in a downstream reactor. Typically, the polycarbonate oligomer produced in the oligomerization stage (eg, the first reaction stage) can be characterized by a number average molecular weight (Mn) of about 1,000 Da to about 7,500 Da. In one or more subsequent polymerization stages (eg, the second reaction stage), the Mn of the polycarbonate can be increased from about 8,000 Da to about 25,000 daltons (measured by using a polycarbonate standard). In general, Mn is represented by the formula 2:

Where N _i is the number of molecules of molecular weight M _i .

  The term “melt polymerization conditions” is understood to mean the conditions necessary to carry out the reaction between a dihydroxy aromatic compound and a diaryl carbonate in the presence of a transesterification catalyst. Usually, no solvent is used in this method, and the reactants (eg, dihydroxy aromatic compound, diaryl carbonate) are in a molten state. In one embodiment, the reaction temperature during melt polymerization can range from about 100 ° C to about 350 ° C, or alternatively from about 180 ° C to about 310 ° C. In one embodiment, the pressure during melt polymerization can be atmospheric, or overpressure, or alternatively from about atmospheric to about 15 torr in the initial stage of the reaction (eg, the first reaction stage), The stage can be at a reduced pressure, eg, about 0.2 torr to about 15 torr. In one embodiment, the reaction time during melt polymerization can be from about 0.1 hours to about 10 hours.

  In one embodiment, diaryl carbonate esters suitable for use in melt polymerization are diphenyl carbonate, activated diphenyl carbonate having an electron withdrawing substituent on the aryl group, bis (4-nitrophenyl) carbonate, Bis (2-chlorophenyl) carbonate, bis (4-chlorophenyl) carbonate, bis (methylsalicyl) carbonate, bis (4-methylcarboxylphenyl) carbonate, bis (2-acetylphenyl) carboxylate, bis (4-acetylphenyl) Carboxylates and the like, or combinations thereof can be included.

  In one embodiment, the catalyst used for the melt polymerization of polycarbonate comprises an alpha catalyst or a beta catalyst. Beta catalysts are usually volatile and decompose at high temperatures. Therefore, the beta catalyst is preferably used in the polymerization stage at a very low temperature. Alpha catalysts are usually more thermally stable and are not as volatile as beta catalysts.

In one embodiment, the alpha catalyst can include an alkali ion source or an alkaline earth ion source. In one embodiment, the source of alkali ions or alkaline earth ions is an alkali metal hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, alkaline earth hydroxide, magnesium hydroxide, calcium hydroxide, etc., or These combinations are included. In one embodiment, the alkali ion or alkaline earth ion source is a corresponding salt of a carboxylic acid (eg, sodium acetate), a derivative of ethylenediaminetetraacetic acid (EDTA) (eg, EDTA tetrasodium salt, EDTA magnesium disodium salt). Or further combinations thereof. Non-limiting examples of alpha transesterification catalysts suitable for use in the present disclosure include alkali or alkaline earth metal salts of non-volatile inorganic acids, NaH ₂ PO ₃ , NaH ₂ PO ₄ , Na ₂ HPO ₃ , KH ₂ PO ₄ , CsH ₂ PO ₄ , Cs ₂ HPO ₄ ; a mixed salt of phosphoric acid, NaKHPO ₄ , CsNaHPO ₄ , CsKHPO _4, etc., or combinations thereof.

In one embodiment, the beta catalyst can include a quaternary ammonium compound, a quaternary phosphonium compound, or the like, or a combination thereof. In one embodiment, the quaternary ammonium compound can be a compound represented by the structure (R ⁴ ) ₄ N ⁺ X ^{−, wherein} each R ⁴ can be the same or different and each R ⁴ is independently A C _1-20 alkyl group, a C _4-20 cycloalkyl group or a C _4-20 aryl group, wherein X ⁻ is an organic or inorganic anion, such as a hydroxide ion, halide, etc. Ion, carboxylate ion, sulfonate ion, sulfate ion, formate ion, carbonate ion or bicarbonate ion. Non-limiting examples of organic quaternary ammonium suitable for use in the present disclosure include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium formate, tetrabutylammonium acetate, or combinations thereof. Including. In one embodiment, the quaternary ammonium compound comprises tetramethylammonium hydroxide. In one embodiment, the quaternary phosphonium compound can be a compound represented by the structure (R ⁵ ) ₄ P ⁺ X ⁻ , wherein each R ⁵ is independently a C _1-20 alkyl group, C _4- Can be a ₂₀ cycloalkyl group or a C _4-20 aryl group, and X ⁻ is an organic or inorganic anion, for example, hydroxide ion, halide ion, carboxylate ion, sulfonate ion, sulfate ion , Formate ion, carbonate ion or bicarbonate ion. When X ⁻ is a polyvalent anion such as carbonate or sulfate, it is understood that the positive and negative charges in the quaternary ammonium and / or phosphonium structures are appropriately balanced. For example, each of R ^{4 to} R ⁵ is a methyl group, and when X ⁻ is a carbonate ion, it is understood that X ⁻ represents 2 (CO ₃ ⁻² ). Non-limiting examples of organic quaternary phosphonium compounds suitable for use in the present disclosure include tetramethylphosphonium hydroxide, tetramethylphosphonium acetate, tetramethylphosphonium formate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate (TBPA), tetraacetate Including phenylphosphonium, tetraphenylphosphonium phenoxide and the like, or combinations thereof. In one embodiment, the organic quaternary phosphonium compound comprises TBPA.

In one embodiment, the amount of alpha catalyst and beta catalyst used can be based on the total number of moles of dihydroxy compound used in the polymerization reaction. When referring to the ratio of beta catalyst (eg phosphonium salt) to all dihydroxy compounds used in the polymerization reaction, it is convenient to refer to the number of moles of phosphonium salt per mole of dihydroxy compound and present in the reaction mixture. Means the number of moles of phosphonium salt divided by the sum of the number of moles of each individual dihydroxy compound. In one embodiment, the alpha catalyst provides about 1 × 10 ⁻² to about 1 × 10 ⁻⁸ , alternatively about 1 × 10 ⁻⁴ to about 1 × 10 ⁻⁷ moles of metal per mole of dihydroxy compound used. Can be used in an amount effective to effect. In one embodiment, the amount of beta catalyst (eg, organic ammonium salt or phosphonium salt) is about 1 × 10 ⁻² to about 1 × 10 ⁻⁵ , or about 1 per total moles of dihydroxy compound in the reaction mixture. It can be made into ^x10 < ^{-3 >-about} 1 * 10 <^-4> mol.

  In one embodiment, the branched polycarbonate block can be prepared by adding a branching agent during polymerization, wherein the branching agent has at least 3 functional groups selected from hydroxyl, carboxyl, carboxylic anhydride and haloformyl. One polyfunctional organic compound. Non-limiting examples of branching agents suitable for use in the present disclosure include trimellitic acid, trimellitic anhydride, trimellitic acid trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC (1,3,3 5-tris ((p-hydroxyphenyl) isopropyl) -benzene), tris-phenol PA (4 (4 (1,1-bis (p-hydroxyphenyl) -ethyl) alpha, alpha-dimethylbenzyl) phenol), 4 -Chloroformyl phthalic anhydride, trimesic acid, benzophenone tetracarboxylic acid, etc., or combinations thereof. In one embodiment, the branching agent can be added to the phosgenation mixture in an amount of about 0.05 wt% to about 5.0 wt%, based on the total weight of the phosgenation mixture. Mixtures comprising linear polycarbonate and branched polycarbonate can be used.

  In one embodiment, all types of polycarbonate end groups are contemplated as useful in polycarbonate compositions, provided that such end groups do not significantly adversely affect the desired properties of the composition. Condition. In one embodiment, a chain terminator (also referred to as a capping agent) can be included during the polymerization. This chain terminator limits the growth rate of the molecular weight and thus controls the molecular weight in the polycarbonate. In one embodiment, the chain terminator can comprise a phenolic compound, a monophenolic compound, a chloromonocarboxylic acid, a monochloroformate, derivatives thereof, and the like, or combinations thereof.

As the non-limiting examples of suitable phenolic compounds for use in the present disclosure is chain terminators include monophenols compounds, monocyclic phenols, phenol, C ₁ -C ₂₂ alkyl-substituted phenols, p- cumyl - phenol, p- and three Secondary butylphenol; monoether of diphenol, p-methoxyphenol; alkyl substituted phenol with branched alkyl substituents having 8 to 9 carbon atoms; monophenol UV absorber, 4-substituted-2-hydroxybenzophenone; salicylic acid Aryl; monoester of diphenol, resorcinol monobenzoate, 2- (2-hydroxyaryl) -benzotriazole, 2- (2-hydroxyaryl) -1,3,5-triazine; derivatives thereof, or combinations thereof Is included.

As the non-limiting examples of suitable monocarboxylic acid chlorides for use in this disclosure chain terminators, monocyclic monocarboxylic acid chlorides, benzoyl chloride, C ₁ -C ₂₂ alkyl-substituted benzoyl chloride, toluoyl chloride, halogen chloride Substituted benzoyl, bromobenzoyl chloride, cinnamoyl chloride, 4-naphthimidobenzoyl chloride; polycyclic monocarboxylic acid chloride, trimellitic anhydride chloride, naphthoyl chloride; combination of monocyclic and polycyclic monocarboxylic acid chloride A chloride of an aliphatic monocarboxylic acid having up to 22 carbon atoms; a chloride of a functionalized aliphatic monocarboxylic acid, acryloyl chloride, methacryloyl chloride; monochloroformate, monocyclic monochloroformate, phenyl chloroformate Alkyl substituted phenyl esters of chloroformate, p-cumyl chloroformate Alkenyl, chloroformate toluene; and derivatives thereof, or combinations thereof.

  In one embodiment, the polycarbonate can be a branched polycarbonate comprising units already described herein, wherein about 3 mol% or more of the portion can be derived from the branching agent relative to the total number of moles of polycarbonate. The end-capping group can be derived from an end-capping agent having a Pka of about 8.3 to about 11. In such embodiments, the branching agent can include trimellitic acid trichloride, 1,1,1-tris (4-hydroxyphenyl) ethane, or combinations thereof, and the end-capping agent is a phenol, cyano group, It can include phenols containing substituents such as aliphatic groups, olefin groups, aromatic groups, halogens, ester groups, ether groups, or combinations thereof. In one embodiment, the end-capping agent comprises phenol, pt-butylphenol, p-methoxyphenol, p-cyanophenol, p-cumylphenol, etc., or combinations thereof.

  In one embodiment, the poly (carbonate-siloxane) copolymer can be made by any suitable method. Methods for preparing poly (carbonate-siloxane) copolymers are described in more detail in US Pat.

  In one embodiment, the ITR-PC-siloxane copolymer can be made by any suitable method. In one embodiment, polycarbonate copolymers comprising arylate ester units can generally be prepared from polyester blocks, which can be prepared by interfacial polymerization as previously described herein. However, rather than utilizing dicarboxylic acids or diols themselves, corresponding acid halides, in particular reactive derivatives of acids or diols such as acid dichlorides and acid dibromides can be used. For example, instead of using isophthalic acid, terephthalic acid or combinations thereof, isophthaloyl dichloride, terephthaloyl dichloride or combinations thereof can be used. Polyesters can also be obtained by condensation of the melt methods described above (eg, melt polymerization), solution phase condensation, or transesterification, for example, dialkyl esters such as dimethyl terephthalate use acid catalysis. Can be transesterified with a dihydroxy reactant to produce a polyester block. Branched polyester blocks can be used that incorporate branching agents (eg, glycols having 3 or more hydroxyl groups; trifunctional or polyfunctional carboxylic acids). As recognized by those skilled in the art and with the aid of the present disclosure, depending on the end use of the composition, it may be desirable to have various concentrations of acid and hydroxyl end groups on the polyester block.

  In one embodiment, the polycarbonate copolymer comprising allylate ester units is about 2,000 Da to about 100,000 Da, or about 3, as measured by GPC using a cross-linked styrene-divinylbenzene column calibrated with polycarbonate standards. It can have a Mw from 000 Da to about 75,000 Da, alternatively from about 4,000 Da to about 50,000 Da, alternatively from about 5,000 Da to about 35,000 Da, or alternatively from about 17,000 Da to about 30,000 Da. GPC samples were prepared at a concentration of 1 milligram per milliliter (mg / ml) and eluted at a flow rate of 1.0 ml / min.

  In one embodiment, the polycarbonate copolymer is about 0.3 dl / g to about 1.5 dl / g, alternatively about 0.4 dl / g to about 1.25 dl / g, or alternatively about Intrinsic viscosities from 0.45 dl / g to about 1.0 dl / g can be characterized.

  In one embodiment, the poly (carbonate-siloxane) is about 1 cubic centimeter per 10 minutes (cc / 10 minutes) to about 50 cc / 10 when measured according to ASTM D1238 at 300 ° C. under a 1.2 kg weight load. A melt volume flow rate of about 1.5 cc / 10 minutes to about 40 cc / 10 minutes, or alternatively about 2 cc / 10 minutes to about 30 cc / 10 minutes can be characterized.

  In one embodiment, the polycarbonate comprises a commercially available polycarbonate, such as, for example, LEXAN FST resin, LEXAN FST3403 resin, LEXAN FST9705 resin, or combinations thereof. LEXAN FST resin is a polycarbonate (PC) copolymer that provides excellent flame retardant, smoke and poison performance. LEXAN FST3403 resin is a high flow PC copolymer resin suitable for injection molding. LEXAN FST9705 resin is a high viscosity PC ester and is commercially available from SABIC Innovative Plastics.

  In one embodiment, the polycarbonate is in the capacitor film polymer composition from about 0.1 weight percent (wt%) to about 99.9 wt%, based on the total weight of the capacitor film polymer composition, or About 1% to about 99%, alternatively about 10% to about 90%, alternatively about 25% to about 75%, alternatively about 40% to about 60%, or alternatively about 45% About 55 wt%, alternatively about 0.1 wt% to about 50 wt%, alternatively about 1 wt% to about 50 wt%, alternatively about 10 wt% to about 50 wt%, or alternatively about 25 wt% to about 50 wt% % Can be present. In one embodiment, the capacitor film polymer composition comprises about 50% by weight polycarbonate.

  In one embodiment, the capacitor film polymer composition comprises, for example, a stabilizer (eg, an antioxidant), a heat stabilizer, a light stabilizer, an ultraviolet (UV) absorption additive, a quencher, a plasticizer, a lubricant. , Lubricants, antistatic agents, flame retardants, anti-drip agents, irradiation stabilizers, fluoropolymers, pigments, dyes, particulate fillers, glass, carbon fiber, mica, talc, additional polymers (eg, amorphous polymers), polyethylene, It further includes an additive to improve one or more properties of the polymer composition, such as high density polyethylene (HDPE), polyethylene terephthalate (PET), fatty acid, siloxane, wax, etc., or combinations thereof. In such embodiments, the additive may be used so that the fluorine does not exceed about 10% by weight, the silicone does not exceed about 5,000 ppm, or otherwise, as desired in the polymer composition. It can be selected so that it does not significantly adversely affect the properties. In one embodiment, the additive can be present in the polymer composition for a capacitor film in an amount that provides less than about 1,000 ppm of a compound having a molecular weight of less than about 250 Da.

  In some embodiments, the polymer composition for a capacitor film comprises, for example, a phosphorus-containing stabilizer, an organic phosphorus compound, a bifunctional phosphorus-containing compound, a phosphite, a triaryl phosphite, a phosphonite, an aryl sulfonate, a sterically hindered phenol, and the like. Or an antioxidant such as a combination thereof. In other embodiments, the polymer composition for a capacitor film does not include a stabilizer, such as a phosphorus-containing stabilizer. In one embodiment, the phosphorus-containing stabilizer can be characterized by a weight average molecular weight of about 300 Da or greater.

  In one embodiment, the polymer composition for a capacitor film can include two or more phosphorus-containing stabilizers. In such embodiments, the phosphorus-containing stabilizers can be the same type or different types. For example, a polymer composition for a capacitor film can include two phosphites, or one phosphite and one phosphonite.

  Non-limiting examples of phosphites and phosphonites suitable for use in the present disclosure include triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert- Til-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-) tert-butyl-phenyl) 4,4′-biphenylenediphosphonite, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6) -Methylphenyl) ethyl phosphite, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'- Diyl) phosphite], 2-ethylhexyl (3,3 ′, 5,5′-tetra-tert-butyl-1,1′-bi) Phenyl-2,2′-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphirane, tetrakis ( 2,4-di-tert-butylphenyl) -4,4-biphenyldiphosphonite, tris (2,4-di-tert-butylphenyl) phosphite (PEPQ), and the like, or combinations thereof.

  In one embodiment, the phosphorus-containing stabilizer is from about 0.005% to about 3%, or alternatively from about 0.01% by weight, based on the total weight of the composition in the polymer composition for capacitor films. It can be present in an amount of about 1.0% by weight.

  In one embodiment, the phosphorus-containing stabilizer is about 0 wt% to about 2 wt%, alternatively about 0 wt% to about 1.0 wt%, based on the total weight of the composition in the capacitor film polymer composition. %, Or alternatively in an amount of from about 0.5% to about 1.0% by weight, and the phosphorus-containing stabilizer can be characterized by a weight average molecular weight of about 500 Da or greater.

  In one embodiment, the phosphorus-containing stabilizer comprises IRGAPHOS 168, which is available from Ciba Chemical Co. Tris-di-tert-butylphenyl phosphite commercially available from In one embodiment, the phosphorus-containing stabilizer comprises DOVERPHOS S-9228, which is manufactured by Dober Chemical Co. Commercially available.

  In one embodiment, the antioxidant comprises a sterically hindered phenol such as, for example, alkylated monophenols, alkylated bisphenols, polyphenols, etc., or combinations thereof.

  Non-limiting examples of alkylated monophenols suitable for use in the present disclosure include 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol; -Tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4- 2- (α-methylcyclohexyl) -4,6-dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol; 2,6-di-tert-butyl -4-methoxymethylphenol; nonylphenol whose side chain is linear or branched; 2,6-di-nonyl-4-methylphenol 2,4-dimethyl-6- (1'-methylundeca-1'-yl) phenol; 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol; 2,4- Dimethyl-6- (1′-methyltridec-1′-yl) phenol and the like, or combinations thereof.

  Non-limiting examples of alkylidene bisphenols suitable for use in the present disclosure include 2,2′-methylene bis (6-tert-butyl-4-methylphenol), 2,2′-methylene bis (6-tert-butyl-4-ethyl) Phenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis ( 6-nonyl-4-methylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2 '-Ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methyl Benzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis- (2,6-di-tert-butylphenol), 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3- tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis ( 5-tert-butyl-4-hydroxy-2-methyl-phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3 '-Tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2) '-Hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1 , 1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane, or combinations thereof

  In one embodiment, the sterically hindered phenol can be characterized by a molecular weight of about 300 Da or greater. In such embodiments, the molecular weight of the sterically hindered phenol can help retain the sterically hindered phenol moiety in the polymer melt at high processing temperatures, such as, for example, temperatures above about 300 ° C.

  In one embodiment, the sterically hindered phenol is about 0.005% to about 2%, or alternatively about 0.01% to about 0.01% by weight, based on the total weight of the composition in the capacitor film polymer composition. It can be present in an amount of 1.0% by weight.

  In some embodiments, the polymer composition for a capacitor film can include one or more particulate fillers to adjust the properties of the composition, such as relative dielectric constant, coefficient of thermal expansion, and the like. In other embodiments, the polymer composition for a capacitor film does not include a particulate filler.

  Non-limiting examples of particulate fillers suitable for use in the present disclosure include silica powder, fused silica, crystalline silica; boron nitride powder, boron-silicate powder; alumina, magnesium oxide (magnesia); silicate sphere. Dust; cenosphere; aluminosilicate (armosphere); natural silica sand; quartz; quartzite; titanium oxide, barium titanate, barium strontium, tantalum pentoxide, tripoly; diatomaceous earth; included. In one embodiment, the particulate filler can be surface treated with silane to improve adhesion and dispersibility with the polymer composition.

  In one embodiment, the particulate filler can be present in the capacitor film polymer composition in an amount effective to provide the desired physical properties. In one embodiment, the particulate filler is about 0.1% to about 50% by volume, or about 0.1% to about 40% by volume, relative to the total volume of the composition in the capacitor film polymer composition. %, Alternatively about 5% to about 30%, alternatively about 5% to about 20% by volume.

  In some embodiments, the polymer composition for a capacitor film can further comprise at least one additional polymer, the additional polymer comprising about 10 or more fluorine or silicon relative to the total weight of the composition. It is selected so as not to result in greater than weight percent or otherwise significantly adversely affect the desired properties of the composition.

  Non-limiting examples of additional amorphous polymers suitable for use in the present disclosure include poly (phenylene sulfone), poly (sulfone), poly (ether sulfone), poly (arylene sulfone), poly (phenylene ether), polycarbonate, poly These blends such as etherimide siloxanes, copolymers thereof, or combinations thereof are included.

  In one embodiment, the additional polymer is about 0 wt% to about 12 wt%, alternatively about 0.1 wt% to about 10 wt%, based on the total weight of the composition in the capacitor film polymer composition. Or, alternatively, can be present in an amount of from about 0.5% to about 5% by weight.

  In some embodiments, the polymer composition for a capacitor film is a composition intended for use in temperature applications above about 200 ° C., for example, fluorinated ethylene propylene (FEP), polytetrafluoroethylene ( PTFE), and fluoropolymers such as perfluoroalkoxy polymers (PFA), and to reduce the coefficient of friction of capacitor films intended for use in temperature applications below about 200 ° C., to improve slipping and for capacitor films As fillers to aid processing, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF) and poly (ethene-co-tetrafluoroethene) (ETFE) can further be included.

  In one embodiment, the additive (excluding any filler) is about 0.005 wt% to about 20 wt%, or alternatively about 0, based on the total weight of the composition in the capacitor film polymer composition. It can be present in an amount from 0.01% to about 10% by weight.

  In one embodiment, polyetherimide and / or polyetherimide sulfone, and polycarbonate, and any optional additives are combined (eg, contact, blend, mix, etc.) and use any suitable mixing means. As a result, a polymer composition for a capacitor film can be obtained. In one embodiment, polyetherimide and / or polyetherimide sulfone, and polycarbonate, and any optional additives can be combined under conditions to form an intimate blend, such conditions being , Melt mixing in a single or twin screw extruder, a mixing bowl, or similar mixing or blending apparatus that can apply shear to the components being brought together. In some embodiments, twin screw extruders may be preferred because twin screw extruders have stronger mixing and self-wiping capabilities than single screw extruders.

  In one embodiment, it may be advantageous to apply a vacuum to the blend composition from at least one vent inlet in the extruder to remove volatile impurities in the composition. In one embodiment, it may be advantageous to dry (eg, contain as little water as possible) the polyetherimide and / or polyetherimide sulfone, and the polycarbonate, and any optional additives prior to melting. .

  In one embodiment, melt processing of the capacitor film polymer composition avoids over-decomposition of the polymer while still allowing sufficient melting to obtain a tight polymer mixture that contains no unblended components. Therefore, it can be performed at a temperature of about 290 ° C to about 360 ° C. In one embodiment, the compounding is such that the residence time of the polymer composition in the machine is short, the temperature can be carefully controlled, and frictional heat is utilized, resulting in an intimate blend between the components. Can be implemented to ensure that

  In one embodiment, the capacitor film polymer composition also has a pore size or aperture size of, for example, from about 1 micron to about 100 microns, alternatively from about 25 microns to about 100 microns, or alternatively from about 40 microns to about 100 microns. Melt filtration can be performed using any suitable polymer filter device, such as a polymer candle filter or screen filter having an undesirable black speck or other non-uniform contaminant, eg, greater than about 1 micron Any particles having a diameter can also be removed. As recognized by those skilled in the art and with the aid of the present disclosure, if the filtration device has a pore size or aperture size of, for example, 1 micron, such a filtration device may be solid particles of a size of 1 micron or larger. All of the above are retained and solid particles having a size of less than 1 micron are passed through. Further, as recognized by those skilled in the art and with the aid of the present disclosure, the size of the solid particles that can be removed are those mentioned with respect to the pore size or aperture size of the filtration device, such solids. It does not relate to the shape of the particles and the associated physical dimensions.

  In one embodiment, polyetherimide and / or polyetherimide sulfone, and polycarbonate, and any optional additives, are placed in an extrusion compounder to produce a continuous thread that is cooled. Can then be cut into pellets (eg, extruded pellets). In another embodiment, polyetherimide and / or polyetherimide sulfone, and polycarbonate, and any optional additives are mixed by dry blending and then milled or extruded into a fluid in a mill. Can be cut into pellets. In yet another embodiment, the polyetherimide and / or polyetherimide sulfone, and polycarbonate, and any optional additives can also be mixed as described in more detail later in this specification. It can be directly extruded to form a film. In yet another embodiment, the pellets of the polymer composition can be melted and then extruded to form a film.

  In one embodiment, the polymer composition for the capacitor film comprises a miscible polymer blend, the polymer composition as measured by differential scanning calorimetry (DSC) from about 125 ° C. to about 250 ° C., alternatively from about 130 ° C. About 240 ° C, alternatively about 135 ° C to about 230 ° C, alternatively about 150 ° C to about 220 ° C, alternatively about 160 ° C to about 210 ° C, alternatively about 170 ° C or higher, alternatively about 180 ° C or higher, alternatively about 190 ° C or higher, Alternatively, it may be characterized by one glass transition temperature (Tg) of about 200 ° C. or higher, alternatively about 210 ° C. or higher, or alternatively about 220 ° C. or higher.

  In general, a miscible polymer blend refers to a mixture of two or more polymers, where the mixed polymer behaves as one phase (eg, behaves as one polymer) when melted together, This mixed polymer exhibits one Tg. In contrast, an immiscible polymer blend refers to a mixture of two or more polymers that, when melted together, phase separate, i.e., the mixed polymer exhibits two or more Tg's. For example, in the case of two miscible polymers, when mixed together, these polymers phase separate and these phases can be dispersed. As recognized by those skilled in the art and with the aid of this disclosure, when two polymers are mixed together, in the case of two polymers, these polymers become miscible to form a miscible polymer blend There are only certain mixing ratios that can be made. In one embodiment, the polyetherimide and / or polyetherimide sulfone and the polymer carbonate disclosed herein can be mixed in any ratio to form a miscible polymer blend. Further, the polyetherimide and polyetherimide sulfone disclosed herein can be mixed in any ratio to form a miscible polymer blend.

  In one embodiment, the polymer composition for a capacitor film can be characterized by the appearance of an extruded pellet, the appearance of the extruded pellet being transparent (eg, free of haze). As recognized by those skilled in the art and with the aid of the present disclosure, when two transparent polymers are blended, the appearance of the resulting blend depends on the miscibility of these polymers. In general, if two transparent polymers are mixed to form a miscible polymer blend, the miscible polymer blend can be transparent. In addition, when two transparent polymers are mixed to form an immiscible polymer blend, the immiscible polymer blend becomes opaque, turbid and non-transparent because the polymer phase separates. obtain.

  In one embodiment, the capacitor film polymer composition has a specific gravity of about 1.25 to about 1.35, alternatively about 1.27 to about 1.33, or alternatively about 1.28 to about 1.31. Can be characterized. In general, specific gravity represents the ratio of the density of a substance to the density of water, where the density of the substance and the density of water are measured at the same temperature. The density of the polymer is generally expressed in g / cc and can be determined according to ASTM D1505.

  In one embodiment, the polycarbonates disclosed herein can have a relatively high specific gravity as compared to the specific gravity of the polyetherimide and / or polyetherimide sulfone disclosed herein. As recognized by those skilled in the art and with the aid of this disclosure, the specific gravity of the polymer composition for capacitor films is higher than the specific gravity of the corresponding polyetherimide and / or polyetherimide sulfone itself, and thus blend ( For example, the free volume in the capacitor film polymer composition) is reduced, and as a result, the electrical performance is improved. Furthermore, as recognized by those skilled in the art and with the aid of this disclosure, free volume in materials is a known failure mechanism in dielectric films made from such materials. In general, the free volume of a substance is considered the volume within the substance in which a given molecule moves freely.

In one embodiment, a capacitor film for polymer compositions, the ratio of the viscosity of the viscosity of 100 sec ^-1 and 5,000Sec ^-1 is from about 1 to about 10 or about 2 to about 9, or alternatively from about 2.5, It can be characterized by about 8.5.

  In one embodiment, the polymer composition for a capacitor film is about 1 cubic centimeter (cc) per 10 minutes (cc) (measured according to ASTM D1238 at 295 ° C. to 337 ° C. under a weight load of 6.7 kilograms (kg). cc / 10 minutes) to about 40 cc / 10 minutes, alternatively about 2.5 cc / 10 minutes to about 35 cc / 10 minutes, alternatively about 4.5 cc / 10 minutes to about 13 cc / 10 minutes, or alternatively about 20 cc / 10 minutes to It can be characterized by a melt volume rate of about 37 cc / 10 minutes.

  In one embodiment, the capacitor film polymer composition is about 100 ° C. to about 225 ° C. as measured according to ASTM D648 at 264 psi (1.8 Mpa) in a 3.2 millimeter (mm) thick sample. Or about 110 ° C to about 215 ° C, alternatively about 115 ° C to about 200 ° C, alternatively about 150 ° C or higher, alternatively about 160 ° C or higher, alternatively about 170 ° C or higher, alternatively about 180 ° C or higher, or about 190 ° C or higher, or Alternatively, it can be characterized by a heat distortion temperature or heat deflection temperature (HDT) of about 200 ° C. or higher. The HDT of a material generally refers to the temperature at which the material deforms under a specified load.

  In one embodiment, the capacitor film polymer composition can be extruded using an extruder conventionally used for thermoplastic compositions using a flat die. In general, an extrusion cast film process involves melting a polymer composition in an extruder to form a molten polymer; conveying the molten polymer to a flat die with a small lip spacing separation to produce a film (eg, an extruded film). Pulling the film onto a take-up roller and stretching the film at a relatively high take-up speed; and cooling / solidifying the polymer in the film to form a final film. The extruder can be a uniaxial or biaxial design, and a melt pump can also be used to cause the polymer through the die to provide a constant non-pulsating flow. In one embodiment, the die can be characterized by a die lip spacing of about 100 microns to about 200 microns. In one embodiment, the take-up roller can be operated at speeds up to about 200 m / min (eg, take-up speed). Capacitor films can be extruded through a flat die and as the film is pulled by a take-up roller, the film is stretched in the direction of film movement (eg, uniaxial stretching) to form a uniaxially stretched capacitor film. can do. In one embodiment, the extruder design can also include an additional heated roll to temper / anneal the film, thus minimizing the occurrence of frozen internal stresses. The edges of the film can be trimmed and the film can be wound on a roll using a tension-controlled winding mechanism.

  In some embodiments, commercially available functionalized fillers and / or experimentally functionalized fillers are uniformly dispersed in the polymer composition (eg, compounded into the polymer composition) to form a composite. The material can be formed and then the composite material can be stretched into a thin film. In such an embodiment, the filler is compounded into the polymer composition to obtain a uniform dispersion after being performed in a separate extruder or alternatively in the same extruder used to melt the polymer. Can be stretched into a film. In one embodiment, compounding the filler into the polymer composition can be done in the same extruder used to melt the polymer and then stretched into a film. As recognized by those skilled in the art and with the help of the present disclosure, the molten polymer is accurately fed into the die in a constant and uniform flow, the rheological properties of the polymer used to make the film, the polymer composition and Both the equipment is clean and the mechanical properties of the winding mechanism contribute to the successful preparation of extruded films having a relatively small thickness (eg, less than about 20 microns).

  In one embodiment, the extruded cast film method can be a one-step method, can be scaled to larger size equipment, and does not require the use of any solvent. Even in the case of relatively high molecular weight and / or high glass transition temperature polymers, this extrusion process (eg, extrusion cast film process) is an excessive temperature that can cause thermal or mechanical degradation of the polymer composition. Can be suitably designed to achieve a polymer environment that does not result in In one embodiment, the use of a filtration device for the molten polymer can produce films that are substantially free of contaminants such as gels and black pieces, and these contaminants are not properly removed from the molten polymer. In some cases, there is a risk of harming the insulation performance of the resulting film. In one embodiment, the film produced by the extrusion cast film method is a thinned film of uniform thickness (eg, less than about 50 microns in thickness and thinner), wrinkles or surface undulations across the width of the film. And can be flat (eg, smooth, wrinkled, etc.) and relatively free of contaminants.

  In one embodiment, the molten polymer can be conveyed to a flat die using a melt pump. In one embodiment, the film can be extruded at a temperature from about 250 ° C to about 500 ° C, or alternatively from about 300 ° C to about 450 ° C. In one embodiment, the extruded film can be uniaxially stretched to produce a dielectric film substrate.

  In one embodiment, forming the capacitor film comprises combining the components of the polymer composition for the capacitor film, melting and intimate mixing to form the molten polymer, filtering the molten polymer to greater than about 1 micrometer. Removing the particles of to form a filtered molten polymer, extruding the filtered molten polymer through a flat die at a temperature of about 250 ° C to about 500 ° C, or alternatively about 275 ° C to about 400 ° C; Forming an extruded film, and uniaxially stretching the extruded film to form a dielectric film substrate (eg, capacitor film, uniaxially stretched capacitor film). After stretching, the capacitor film can be wound on a take-up roll for metallization or storage or transportation as described in more detail later in this specification. As recognized by those skilled in the art and with the aid of the present disclosure, the composition and method of making a capacitor film can be varied to achieve the desired performance characteristics, particularly electrical characteristics.

  In one embodiment, the capacitor film can have a film length of about 10 meters or more, alternatively greater than about 100 meters, or alternatively greater than about 10,000 meters. In one embodiment, the capacitor film can have a film width of about 300 mm or greater, alternatively greater than about 300 mm, or alternatively greater than about 3,000 mm.

  As recognized by those skilled in the art and with the aid of the present disclosure, the rate at which the film can be extruded can vary. In one embodiment, the rate at which the capacitor film can be extruded can be from about 10 lbs / hr (4.5 kg / hr) to about 1000 lbs / hr (500 kg / hr).

  In one embodiment, the winding speed (e.g., the speed at which the capacitor film can be pulled from the extruder die plate) is from about 10 meters / minute (m / minute) to about 300 m / minute, alternatively from about 50 m / minute to It can range from about 275 m / min, or alternatively from about 100 m / min to about 250 m / min.

  In one embodiment, the capacitor film comprises a high yield extruded film, and the capacitor film (eg, high yield extruded capacitor film) is prior to entering an extruder used to produce the capacitor film. Relative to the total weight of the miscible polymer blend (e.g., the total weight of polyetherimide and / or polyetherimide sulfone and polycarbonate present in the polymer composition for the capacitor film), e.g., prior to extrusion More than about 90 wt.%, Alternatively more than about 92 wt.%, Alternatively more than about 94 wt.%, Alternatively about 96 wt.% Of the polyetherimide and / or polyetherimide sulfone and polycarbonate present in the polymer composition for capacitor films. More than% by weight, or alternatively about 9 Including the weight percent. In one embodiment, the capacitor film comprises a uniaxially stretched high yield extruded capacitor film.

  In one embodiment, the capacitor film has two surfaces (eg, two opposing surfaces), eg, a first film surface and a second film surface. In one embodiment, at least one side of the capacitor film (eg, the first film side, the second film side) can be metallized and a metal layer is deposited on at least a portion of the film to form the metallization. A capacitor film can be obtained. In one embodiment, the capacitor film can be metallized on at least a portion of at least one side of the capacitor film (eg, first film side, second film side), and at least one side of the capacitor film is smooth It can be a good surface. In general, the smooth surface of a capacitor film has an average surface roughness (Ra) of less than about +/− 3%, as determined by optical profilometry, as described in more detail later in this specification. It refers to the surface it has.

  As recognized by those skilled in the art and with the aid of this disclosure, various metals may be used to metalize the capacitor film, depending on the intended use of the film. Non-limiting examples of metals (eg, conductive metals) suitable for use in the present disclosure include copper, aluminum, silver, gold, nickel, zinc, titanium, chromium, vanadium, tantalum, niobium, brass, etc., or these Combinations are included.

  In one embodiment, a method for metallizing a capacitor film comprising a polymer composition includes vacuum metal deposition, high temperature vacuum deposition, chemical vapor deposition, atomic layer deposition, metal sputtering, plasma treatment, electron beam treatment, chemical oxidation reaction or reduction. Reaction, electroless wet chemical vapor deposition and the like, or combinations thereof. In one embodiment, the capacitor film can be metallized on both sides by electroless plating. In another embodiment, a patterned metal layer can be formed on the surface of the capacitor film, for example, by ink jet printing.

  As recognized by those skilled in the art and with the aid of this disclosure, the thickness of the metal layer is determined by the intended use of the metallized film. In one embodiment, the metal layer deposited on the capacitor film is from about 1 angstrom to about 1,000 nanometers, alternatively from about 1 angstrom to about 500 nanometers, alternatively from about 1 angstrom to about 10 nanometers, alternatively from about 1 The thickness of the metal layer from angstroms to about 3,000 angstroms, alternatively from about 1 angstroms to about 2,820 angstroms, alternatively from about 1 angstroms to about 2,000 angstroms, or alternatively from about 1 angstroms to about 1,000 angstroms. Can be characterized.

  In one embodiment, the metal layer deposited on the capacitor film includes a conductive metal. In such embodiments, the metal layer has a resistivity of from about 0.1 to about 1,000 ohm / square, alternatively from about 0.1 to about 500 ohm / square, as measured in accordance with ASTM D257. Squares, or alternatively from about 0.1 to about 100 ohms / square.

  In one embodiment, the surface of the capacitor film to be metallized can be pretreated, for example, to enhance the adhesion of the metal layer. Non-limiting examples of film pretreatment methods suitable for use in the present disclosure include cleaning, flame treatment, plasma discharge, corona discharge, etc., or combinations thereof.

  In one embodiment, one or more additional layers are deposited on the metal layer, for example, a clear coat (eg, poly (methyl methacrylate) and / or poly (ethyl methacrylate) to provide scratch resistance). And / or may be deposited on another layer of a film of polymer composition (eg, polyetherimide, polyetherimide sulfone, polycarbonate, or combinations thereof) to form a laminate.

  In one embodiment, the capacitor film is about 125 ° C. to about 250 ° C., alternatively about 130 ° C. to about 240 ° C., alternatively about 135 ° C. to about 230 ° C., alternatively about 150 ° C. as measured by differential scanning calorimetry (DSC). To about 220 ° C, alternatively about 160 ° C to about 210 ° C, alternatively about 170 ° C or higher, alternatively about 180 ° C or higher, alternatively about 190 ° C or higher, alternatively about 200 ° C or higher, alternatively about 210 ° C or higher, or alternatively about 220 ° C or higher. Tg (for example, one Tg).

  In one embodiment, the polyetherimide and / or polyetherimide sulfone, and poly (carbonate-arylate ester) are each in an amount effective to provide one glass transition temperature of the capacitor film, the polymer composition for the capacitor film. Can be present in a product (eg, a miscible polymer blend).

  In one embodiment, the capacitor film can be characterized by the appearance of a film that is transparent (eg, non-hazy). As recognized by those skilled in the art and with the aid of the present disclosure, the appearance of the resulting film can be transparent when the film is prepared from a clear miscible polymer blend. The appearance of the film can be evaluated by visual inspection of the film surface.

  In one embodiment, polyetherimide and / or polyetherimide sulfone and poly (carbonate-arylate ester) are each present in the polymer composition for a capacitor film in an amount effective to provide a miscible polymer blend. can do.

  In one embodiment, the capacitor film has a thickness of about 100 ° C. to about 225 ° C., or about 110, as measured according to ASTM D648 at 264 psi (1.8 Mpa) in a 3.2 millimeter (mm) thick sample. ℃ to about 215 ℃, alternatively about 115 ℃ to about 200 ℃, alternatively about 150 ℃ or more, alternatively about 160 ℃ or more, alternatively about 170 ℃ or more, alternatively about 180 ℃ or more, alternatively about 190 ℃ or more, or alternatively about 200 ℃ It can be characterized by the above HDT.

  In one embodiment, the capacitor film (e.g., capacitor film, metallized capacitor film) is about 0% to about 2%, or about 0, as measured by dielectric spectroscopy at 1 kHz, 23 [deg.] C and 50% relative humidity (RH). The dielectric loss tangent (Df) of 0.1% to about 1.5%, alternatively about 0.1% to about 1%, or alternatively about 0.1% to about 0.5%. it can. Df can also be referred to as loss factor or dielectric loss factor and generally refers to the dissipating power as heat by the dielectric. Df can be measured according to ASTM D150. RH can generally be defined as the ratio of the partial pressure of water vapor to the equilibrium water vapor pressure at a given temperature.

  In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) is about 0% to about 1%, or about 0.1%, as measured by dielectric spectroscopy at 1 kHz, 23 ° C. and 50% RH. A dielectric loss tangent (Df) of about 0.75%, or alternatively about 0.1% to about 0.5%.

  In one embodiment, the Df of the capacitor film may remain essentially unchanged as the temperature increases, e.g., any change in Df due to an increase or decrease in temperature will cause the physics of the capacitor comprising such a capacitor film. It does not adversely affect and / or interfere with the characteristics and / or electrical characteristics. In one embodiment, the Df of the capacitor film is about 0 ° C to about 200 ° C, alternatively about 0 ° C to about 185 ° C, alternatively about 0 ° C to about 175 ° C, alternatively about 0 ° C to about 170 ° C, or alternatively about 0. At temperatures between 0 ° C. and about 150 ° C., it remains essentially unchanged.

  In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) is about 2 to about 5, or about 3 to about 5 as measured according to ASTM D150 at 1 kHz, 23 ° C. and 50% RH. Or about 2.5 to about 4.5, or alternatively about 3 to about 4, relative dielectric constant (Dk). In general, Dk refers to the ability of a material to store charge when used as a capacitor dielectric. Since Dk is measured as a ratio, it is a dimensionless value.

  In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) is up to the Tg of the polymer composition used to produce the capacitor film, or the polymer composition used to produce the capacitor film. It can be characterized by a stable Dk value up to about 10 ° C. below the Tg of the product, or up to about 20 ° C. below the Tg of the polymer composition used to produce the capacitor film. . In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) is up to about 250 ° C, up to about 240 ° C, alternatively up to about 230 ° C, alternatively up to about 220 ° C, alternatively up to about 210 ° C, or up to about Up to 200 ° C, alternatively up to about 190 ° C, alternatively up to about 180 ° C, alternatively up to about 175 ° C, alternatively up to about 170 ° C, or alternatively up to about 150 ° C, can be characterized by a stable Dk value.

  In one embodiment, the Dk of the capacitor film may remain essentially unchanged as the temperature increases, e.g., any change in Dk due to an increase or decrease in temperature may result in the physics of the capacitor comprising such a capacitor film. It does not adversely affect and / or interfere with the characteristics and / or electrical characteristics. In one embodiment, the Dk of the capacitor film is about 0 ° C. to about 200 ° C., alternatively about 0 ° C. to about 185 ° C., alternatively about 0 ° C. to about 175 ° C., alternatively about 0 ° C. to about 170 ° C., or alternatively about 0 At temperatures between 0 ° C. and about 150 ° C., it remains essentially unchanged. In some embodiments, the Dk of the capacitor film is within a temperature range from about 0 ° C. to the approximate Tg of the polymer composition used to produce the capacitor film, or alternatively from about 0 ° C. to about 200 ° C., Alternatively, less than about 20%, or less than about 10% for the highest Dk value within the temperature range of about 0 ° C to about 190 ° C, alternatively about 0 ° C to about 170 ° C, or alternatively about 0 ° C to about 150 ° C. Or, alternatively, may vary by less than about 10%.

  In one embodiment, a capacitor film (eg, capacitor film, metallized capacitor film) can be characterized by having at least one region that is not wrinkled (eg, a region that is not wrinkled). Is sufficiently flat and smooth so that the surface of the capacitor film is metallized, which advantageously has a consistent surface morphology.

  In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) is less than about 50 microns, alternatively less than about 40 microns, alternatively less than about 30 microns, alternatively less than about 20 microns, alternatively less than about 15 microns, or Alternatively, it may be characterized by a film thickness of less than about 10 microns. In one embodiment, the capacitor film is about 0.1 microns to about 50 microns, alternatively about 0.1 microns to about 20 microns, alternatively about 0.1 microns to about 15 microns, alternatively about 0.1 microns to about 10 microns. It may be characterized by a film thickness of microns, or alternatively from about 0.1 microns to about 7 microns.

  As recognized by those skilled in the art and with the aid of the present disclosure, the thickness of the film can be uniform and varied throughout the wrinkled area. In general, the flatness of wrinkled areas of a capacitor film can be determined by measuring the variation in film thickness across a particular area. For purposes of the disclosure herein, less than about +/− 10% of the film thickness relative to the average thickness of the film over a particular measurement area, or less than about +/− 9% of the film thickness, or Less than about +/− 8% of the film thickness, or less than about +/− 7% of the film thickness, or less than about +/− 6% of the film thickness, or about +/− of the film thickness. Less than -5%, or less than about +/- 4% of the film thickness, or less than about +/- 3% of the film thickness, or less than about +/- 2% of the film thickness, or alternatively A capacitor film (eg, capacitor film, metallized capacitor film) is considered “flat” if it is characterized by a variation in film thickness that is less than about +/− 1% of the film thickness. It can be. In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) has a film thickness that is less than about +/− 1% of the film thickness relative to the average thickness of the film over a particular measurement area. It can be characterized in that it is a variation of.

  In general, the smoothness of a wrinkle-free region of the film surface can be quantified by measuring the average surface roughness (Ra) of the surface by an optical shape measurement method. In general, surface roughness refers to defining surface irregularities. Ra provides an average of the individual heights and depths of such surface irregularities. For the purposes of this disclosure, capacitor films (eg, capacitor films, metallized capacitor films) are measured by optical profilometry, less than about +/− 3%, or about If it is characterized by less than +/− 2% or less than about +/− 1% Ra, it can be considered free of wrinkles. In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) has a Ra of less than about +/− 3% relative to the average film thickness as measured by optical profilometry. Can be a feature.

  In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) has a film thickness that is less than about +/− 10% of the film thickness relative to the average film thickness over a particular measurement area. And an Ra of less than about +/− 3% relative to the average thickness of the film as measured by optical profilometry.

  In general, a capacitor film can be characterized by a film surface area, which represents the total area of the capacitor film, including the first film surface area and the second film surface area.

  In one embodiment, wrinkle free areas can be created over a large film surface area. In one embodiment, at least about 80%, alternatively at least about 85%, alternatively at least about 90%, alternatively at least about 95%, or alternatively at least about 97% of the total surface area of the film can be wrinkle free. .

In another embodiment, the wrinkled area is at least about 1 square meter (m ² ), alternatively at least about 2 m ² , alternatively at least about 3 m ² , alternatively at least about 5 m ² , alternatively at least about 10 m ² , alternatively at least about 20 m ^2. Or at least about 50 m ² , or alternatively at least about 100 m ² , having continuous wrinkle free areas.

  As recognized by those skilled in the art and with the help of the present disclosure, significant manufacturing advantages in that metalized capacitor films can be manufactured, stored, and transported in roll form with large size wrinkle free areas. Is brought about.

  In one embodiment, the capacitor film has a film length from about 1 meter (m) to about 10,000 m, alternatively from about 10 m to about 1,000 m, or alternatively from about 100 m to about 10,000 m, or alternatively from about 100 m to about 500 m. It can be characterized by being. In one embodiment, the capacitor film has a film width of about 100 mm to about 3,000 mm, alternatively about 200 mm to about 2,000 mm, alternatively about 300 mm to about 3,000 mm, or alternatively about 100 mm to about 1,000 mm. Can be characterized.

  In one embodiment, the capacitor film can have a film length of at least about 10 m and a film width of at least about 300 mm, and at least about 80%, alternatively at least about 85%, alternatively at least about 90% of the total surface area of the film. Alternatively, at least about 95%, or alternatively at least about 97% can be wrinkle free.

  In another embodiment, the capacitor film can have a film length of about 10 m to about 10,000 m and a film width of about 300 mm to about 3,000 mm, and at least about 80% of the total surface area of the film, or at least About 85%, alternatively at least about 90%, alternatively at least about 95%, or alternatively at least about 97% can be wrinkle free.

  In one embodiment, the wrinkle free area is sufficiently smooth and flat so that the capacitor film is metallized resulting in a metallized capacitor film with substantially uniform breaking strength (BDS) throughout the area. be able to. In one embodiment, the wrinkled areas are metallized with a BDS of at least 300 volts / micrometer (V / micron), as described in more detail later herein, with the capacitor film being metallized. It can be sufficiently smooth and flat to provide a capacitor film.

In one embodiment, the capacitor film (e.g., non-metallized capacitor film) is about 100 V / micron to about 1,500 V as measured according to ASTM D149 for a 10 micron film at 23 [deg.] C and 50% RH. / Micron, or about 200 V / micron to about 1,250 V / micron, alternatively about 300 V / micron to about 1,000 V / micron, alternatively about 500 V / micron to about 800 V / micron, or alternatively about 600 V / micron to about 800 V / micron. It can be characterized by being a micron BDS. In general, BDS represents the maximum electric field (eg, energy density) that can withstand until a material breaks down. As recognized by those skilled in the art and with the aid of the present disclosure, improvements in electrical properties (eg, Dk, BDS, etc.) significantly increase energy density based on the following theoretical equation (3):
Energy density = 1/2 ^* εo ^* Dk ^* BDS ² (3)
(In the equation, the linear law and the power law respectively describe the relationship between the energy density, Dk, and BDS, and εo is a constant representing the permittivity of free space). As recognized by those skilled in the art and with the aid of the present disclosure, it is particularly difficult to increase the BDS of a material at high temperatures and high frequencies without affecting other properties, ie, Dk and Df. It should be noted that a 25% improvement in BDS improves the energy density by 56% while the change in Dk varies linearly.

  In one embodiment, the difference in BDS of the capacitor film from about 0 ° C. to about 200 ° C., alternatively from about 0 ° C. to about 190 ° C., alternatively from about 0 ° C. to about 170 ° C., or alternatively from about 0 ° C. to about 150 ° C. is 23 Measured in accordance with ASTM D149 at 0 ° C. can result in a BDS value of less than about 40%, alternatively less than about 30%, alternatively less than about 20%, or alternatively less than about 10%.

  In one embodiment, the capacitor film (eg, non-metalized capacitor film) is 1 kHz and from about 0 ° C. to about 200 ° C., alternatively from about 0 ° C. to about 190 ° C., alternatively from about 0 ° C. to about 170 ° C., or alternatively from about 0 From about +/− 5%, alternatively less than about +/− 4%, or alternatively less than about +/− 3% relative to the capacitance value at 23 ° C. . In general, capacitance refers to the ability of a material to store charge.

  In one embodiment, a capacitor film (eg, a capacitor film, a metallized capacitor film) has a metallized surface (eg, an aluminum surface) and / or a dynamic friction coefficient of the capacitor film itself as measured according to ASTM D1894, Less than about 0.75, alternatively less than about 0.6, or alternatively less than about 0.5. In general, the coefficient of dynamic friction, also called the coefficient of friction or sliding friction, or the coefficient of friction, is a measure of how much friction force exists between two solids, for example between two solid surfaces.

  In one embodiment, a capacitor film (eg, a capacitor film, a metallized capacitor film) has a metallized surface (eg, an aluminum surface) and / or a static coefficient of friction of the capacitor film itself measured according to ASTM D1894, Less than about 0.75, alternatively less than about 0.6, or alternatively less than about 0.5. In general, the coefficient of static friction is a measure of how much friction force exists between two solids, for example between two solid surfaces, when neither surface moves.

  In one embodiment, the capacitor film (e.g., capacitor film, metallized capacitor film) is measured from about 0.4 N / mm to about about 0.5 N / mm when measured according to ASTM D1938 using a test specimen having a thickness of 20 microns. It has a longitudinal (MD) trouser tear strength of 3.5 N / mm, alternatively about 0.5 N / mm to about 3.0 N / mm, or alternatively about 1 N / mm to about 2.5 N / mm. can do. In one embodiment, the capacitor film (e.g., capacitor film, metallized capacitor film) is measured from about 0.4 N / mm to about about 0.5 N / mm when measured according to ASTM D1938 using a test specimen having a thickness of 20 microns. It has a transverse (TD) trouser tear strength of 3.5 N / mm, alternatively about 0.5 N / mm to about 3.0 N / mm, or alternatively about 1 N / mm to about 2 N / mm. Can do. Trouser tear strength refers to the average force required to propagate the tear at a constant tear rate over the entire specimen divided by the thickness of the specimen, used for films with a thickness of less than 1 mm Is done. The tear can be propagated to either MD or TD.

  In one embodiment, the capacitor film has a carbon / (oxygen + hydrogen) (C / (O + H)) ratio of less than about 1.35, alternatively less than about 1.30, or alternatively less than about 1.25. It can be. For example, the C / (O + H) ratio for polyetherimide (PEI) is about 1.23, for polyetherimide sulfone (PEIS), about 1.11, and for ITR-PC-Si, about 1.10 for polyethylene naphthalate (PEN), about 0.83 for polyethylene terephthalate (PET), and about 0.92 for polyphenylenesulfone (PPSU) In the case of polypropylene (PP), it is about 0.50. Further, for example, polyphenylene sulfide (PPS), a material known to have poor dielectric performance, has a C / (O + H) ratio of about 1.50. The C / (O + H) ratio can be important in terms of the cleaning process when it comes to char formation. In general, cleansing, also known as self-healing, refers to removing defects caused by pinholes, film flaws or external voltage transients. The heat generated by the arc during the failure considerably evaporates the metallization film of the film around the defect, thereby isolating it by removing the short circuit condition. Heat from the cleaning process can lead to char formation. While not wishing to be bound by theory, as in the case of PPS, if the C / (O + H) ratio is too high, for example 1.5, the carbon (eg char) is in a thick layer It can deposit, increase the insulation resistivity, and power can be more easily dissipated, which is undesirable.

  In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) can be essentially solvent free, ie, less than about 1,000 ppm, based on the total weight of the capacitor film, or Contains less than about 750 ppm, alternatively less than about 500 ppm, or alternatively less than about 250 ppm of a solvent (eg, a compound having a Mw of less than about 250 Da).

In one embodiment, a capacitor film (e.g., capacitor films, metallized capacitor film), without expansion, when viewed at a distance of 0.3 m, over at least about 3m ² area, or at least about 9m ² area, There may be no observable pieces or gels.

In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) is less than two, or alternatively less than one carbonized inclusion having a diameter greater than about 20 microns in an area of 100 cm ^2. inclusion).

In one embodiment, the capacitor film (eg, capacitor film, metallized capacitor film) comprises less than two or alternatively less than one gel area having a diameter greater than about 20 microns in an area of 100 cm ² .

In one embodiment, a capacitor film (e.g., capacitor films, metallized capacitor film), when viewed in the 50 × enlargement, over at least about 3m ² area, or over at least about 9m ² area, observable void Cannot have.

In one embodiment, a uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprises polyetherimide and poly (carbonate-arylate ester), the polyetherimide comprising an aromatic dianhydride, m A unit derived from polymerization with a diamine containing phenylenediamine, p-phenylenediamine or a combination thereof, the polyetherimide being end-capped with a substituted or unsubstituted aromatic primary monoamine, (Carbonate-arylate ester) contains different bisphenol carbonate repeating units and arylate ester repeating units, and the high yield extruded capacitor film is solvent free and is used to produce the capacitor film. Enter the machine And about 90% by weight or more of the miscible polymer blend entering the extruder, and the capacitor film has a film thickness of from about 0.1 microns to about 20 microns. The polyetherimide has a weight average molecular weight of about 20,000 Da to about 400,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity and 5,000Sec ^-1 of 100 sec ^-1 it is less than about 10, polyetherimides, as determined according to ASTM D638, of about 380, It has a tensile modulus of at least 000 psi (2,618 MPa) -Bonate-arylate ester) has a weight average molecular weight of about 2,000 Da to about 100,000 Da as measured by GPC using a polycarbonate standard, and poly (carbonate-arylate ester) is chloroform at 25 ° C. Measured in, having an intrinsic viscosity of about 0.3 dl / g to about 1.5 dl / g, the capacitor film has a glass transition temperature of greater than about 175 ° C. .2 millimeter (mm) thick sample has a heat distortion temperature of about 150 ° C. or higher when measured in accordance with ASTM D648 at 264 psi (1.8 Mpa), and the capacitor film is 1 kHz, 23 Measured according to ASTM D150 at ℃ and 50% RH, about 3 The capacitor film has a dielectric loss tangent of about 0.1% to about 0.5% when measured at 1 kHz, 23 ° C. and 50% RH. Having a breaking strength of about 500 V / micron to about 800 V / micron, measured at 23 ° C. according to ASTM D149, the capacitor film has an average film thickness over a specific measurement area. Having a wrinkle free area having a film thickness variation of less than about +/− 10% of the film thickness, and the capacitor film is measured relative to the average film thickness as measured by optical profilometry , Having an average surface roughness (Ra) of less than about +/− 3%. In such embodiments, the polyetherimide can further comprise polyetherimide sulfone.

  In one embodiment, a method of producing a uniaxially stretched high yield extruded capacitor film, such as the film described in the above paragraph, comprises (a) combining polyetherimide and poly (carbonate-arylate ester): Forming a miscible polymer blend, wherein the poly (carbonate-arylate ester) comprises an ITR-PC-siloxane copolymer, wherein the ITR-PC-siloxane copolymer comprises from about 1 mol% to about 20 mol% bisphenol- An amount of Formula XXIIb-2 effective to provide A carbonate units, about 60 mol% to about 90 mol% of ITR ester units represented by Formula XVIIIc, and about 0.1 wt% to about 10 wt% siloxane units. Containing polysiloxane units represented by mol Is based on the total number of moles of units in the copolymer, and weight percent is based on the total weight of the copolymer, step (b) melting and mixing the miscible polymer blend to form a molten polymer (C) filtering the molten polymer to remove particles greater than about 1 micron to form a filtered molten polymer; (d) the filtered melt at a temperature of about 250 ° C to about 500 ° C. Extruding the polymer with a flat die to form a high yield extruded capacitor film, the high yield extruded capacitor film entering an extruder used to produce the capacitor film Comprising about 90% or more by weight of the miscible polymer blend entering the extruder, based on the total weight of the previous miscible polymer blend, And (e) uniaxially stretching the high yield extruded capacitor film to form a uniaxially stretched high yield extruded capacitor film, wherein the uniaxially stretched high yield extruded capacitor film is further metallized And winding to form a wound metallized capacitor film.

In one embodiment, a uniaxially stretched high yield extruded capacitor film comprising a miscible polymer blend comprises polyetherimide sulfone and poly (carbonate-arylate ester), wherein the polyetherimide sulfone comprises an aromatic dianhydride and , Containing units derived from polymerization with a diamine containing diaminodiphenylsulfone and end-capped with a substituted or unsubstituted aromatic primary monoamine, wherein the poly (carbonate-arylate ester) comprises different bisphenol carbonate repeating units and The high yield extruded capacitor film comprising arylate ester repeat units is solvent free and is based on the total weight of the miscible polymer blend prior to entering the extruder used to produce the capacitor film. The extrusion The capacitor film has a film thickness of from about 0.1 microns to about 20 microns, and the polyetherimide sulfone uses a polystyrene standard. Determined by gel permeation chromatography (GPC) to have a weight average molecular weight of about 20,000 Da to about 400,000 Da, and polyetherimide sulfone is 100 sec ^{−1 as} measured by capillary rheometry at 340 ° C. And the ratio of the viscosity of 5,000 sec ⁻¹ is less than about 10 and the polyetherimide sulfone has a tensile modulus of about 380,000 psi (2,618 MPa) or more, as determined according to ASTM D638. Poly (carbonate-arylate ester) Ter) has a weight average molecular weight of about 2,000 Da to about 100,000 Da as measured by GPC using a polycarbonate standard and poly (carbonate-arylate ester) is measured in chloroform at 25 ° C. Thus, having an intrinsic viscosity of about 0.3 dl / g to about 1.5 dl / g, the capacitor film has a glass transition temperature of greater than about 175 ° C., and the capacitor film is 3.2 millimeters (Mm) thickness of the sample, measured at 264 psi (1.8 Mpa) according to ASTM D648, has a heat distortion temperature of about 150 ° C. or higher, and the capacitor film is 1 kHz, 23 ° C. and 50 When measured according to ASTM D150 at% RH, it has a relative dielectric constant of about 3 to about 5. The capacitor film has a dielectric loss tangent of about 0.1% to about 0.5% when measured at 1 kHz, 23 ° C. and 50% RH, and the capacitor film conforms to ASTM D149 at 23 ° C. When measured, it has a breaking strength of about 500 V / micron to about 800 V / micron, and the capacitor film is about +/− 10% of the film thickness relative to the average thickness of the film over a specific measurement area. The capacitor film has a wrinkle free area with a film thickness variation of less than, and the capacitor film has an average surface of less than about +/− 3% relative to the average film thickness as measured by optical profilometry It has roughness (Ra).

  In one embodiment, a method of producing a uniaxially stretched high yield extruded capacitor film, such as the film described in the above paragraph, combines (a) polyetherimide sulfone and poly (carbonate-arylate ester). Forming a miscible polymer blend, wherein the poly (carbonate-arylate ester) comprises an ITR-PC-siloxane copolymer, wherein the ITR-PC-siloxane copolymer comprises from about 1 mol% to about 20 mol% bisphenol- An amount of Formula XXIIb-2 effective to provide A carbonate units, about 60 mol% to about 90 mol% of ITR ester units represented by Formula XVIIIc, and about 0.1 wt% to about 10 wt% siloxane units. Containing polysiloxane units represented, ol% is based on the total number of moles of units in the copolymer and weight% is based on the total weight of the copolymer, step (b) melting and mixing the miscible polymer blend, Forming, (c) filtering the molten polymer to remove particles greater than about 1 micron to form a filtered molten polymer, (d) the filtration at a temperature of about 250 ° C to about 500 ° C. Extruding the spent molten polymer with a flat die to form a high yield extruded capacitor film, wherein the high yield extruded capacitor film is used to produce the capacitor film Comprising at least about 90% by weight of the miscible polymer blend entering the extruder, based on the total weight of the miscible polymer blend prior to entering. And (e) uniaxially stretching the high yield extruded capacitor film to form a uniaxially stretched high yield extruded capacitor film, the uniaxially stretched high yield extruded capacitor film further comprising a metal Forming a wound metallized capacitor film.

In one embodiment, the capacitor film disclosed herein can be used for any amorphous film application, but is particularly suitable for metallization. In one embodiment, the metallized capacitor film can be used for any metallized film application, but is particularly suitable for electronic applications, for example, as a capacitor or short circuit material. High energy density (eg, greater than about 1 J / cm ³ ), high voltage (eg, greater than about 150 V), non-polar capacitors can be rolled into a cylindrical shape (eg, wound metallized capacitor film) or laminated It can be made using a metallized polymer film that has been converted to a rectangular or square shape (eg, laminated film capacitor, die-type film capacitor).

  In one embodiment, the capacitor films disclosed herein include, but are not limited to, electronic articles such as, for example, capacitors (eg, automotive inverter capacitors, automotive converter capacitors, etc.). Can be formed into various articles.

  In one embodiment, the capacitor film polymer composition is extruded and then deposited on a moving polymer film in a vacuum chamber with a conductive metal, such as copper or aluminum, by about 1 angstrom by vacuum deposition. It can be metallized by spraying to a metal layer thickness of from about 1 to about 1,000 nanometers, alternatively from about 1 angstrom to about 3,000 angstrom, or alternatively from about 1 angstrom to about 1,000 angstrom. The resistivity of the metal layer on the capacitor film can range from about 0.1 ohm / square to about 100 ohm / square. The polymer film can be appropriately masked before the metallization process is performed to provide an unmetallized margin at the width edge of the film, resulting in alternating layers of metallized film (capacitors are When assembled, when the end metallization is finally applied, the opposite edge can have a non-metallized region to prevent shorting of the capacitor electrodes.

  In one embodiment, the capacitor can be manufactured by winding two laminated metallized polymer films into a cylinder. An electrical wire can then be connected to each metal layer. In one embodiment, two individual rolls of metallized film can be placed on a capacitor wrap and wound tightly together on a mandrill (which may subsequently be removed) so that the layer is Arranged in the order of polymer composition / metallized layer / polymer composition / metallized layer, the typical structure of a capacitor is replicated, ie a dielectric having two metal layers on opposite sides. In one embodiment, the capacitor comprises a wound metallized capacitor film. Two rolls of film can be wound with a non-metallized margin on both opposing sides.

  As recognized by those skilled in the art and with the help of the present disclosure, the degree to which the capacitor is wound depends on the physical size of the desired capacitor or the desired capacitance. Tightly rolling the two rolls helps remove any trapped air that could otherwise cause premature failure. Individual capacitors are processed in at least a class 100 clean room environment incorporating HEPA filters to reduce the possibility of contamination by foreign particles at the contact points between dielectric film layers and to reduce moisture uptake in the dielectric. can do. Electrical wrapping can be used to maintain a uniform and good tension on each capacitor. The capacitor is then taped at this edge and secured to an open tray on both sides to prevent the film layer from being wrapped and the cylinder edge or both ends to be covered with a conductive element, such as a conductive metal. It becomes possible to spray. When direct current (DC) is applied, the first spray is made using a solder with a high zinc content and then a normal, softer end spray solder consisting of 90% tin, 10% zinc. solder) can be used. The first spray rubs the metal surface to create grooves and achieves metallization and good contact on the dielectric film. Combining end sprays further aids good adhesive contact with the final termination. Subsequently, conductive (eg, aluminum) lead can then be plated at each end to form the final termination. One end can be spot welded to the bottom of the can, while the other end can be parallel welded to the lid. The capacitor can be filled and closed with a liquid impregnation (eg, isopropylphenylsulfone) in a vacuum filling device.

  In another embodiment, the electronic article can include a capacitor made from a wound metallized uniaxially stretched extruded film (eg, metallized capacitor film, wound metallized capacitor film).

  Other capacitor configurations are possible as recognized by those skilled in the art and with the aid of the present disclosure. For example, the capacitor comprises at least first and second electrodes arranged in a stacked configuration, and a capacitor film arranged between the first and second electrodes, each of the electrodes It can have a flat configuration including a capacitor film that is at least partially disposed in contact. Additional capacitor films and electrode layers can be present in the alternating layers. In one embodiment, a multilayer article for forming an electronic device can include a polymer composition layer / metal layer / dielectric layer, wherein the dielectric layer comprises a capacitor film as disclosed herein, Or it can be another dielectric material. Additional layers (eg, additional alternating dielectric layers / metal layers) can optionally be present.

  In some embodiments, capacitor films (eg, metallized capacitor films) can be laminated to form a laminated film capacitor. The metallized capacitor film can be coated with an adhesive (eg, wax) prior to lamination. When laminating a metallized capacitor film, a non-metallized capacitor film or a sheet that is not metallized can be applied to the top and / or bottom of the metallized capacitor film laminate, and the resulting laminate is Further compression and heating promotes the bonding of the sheets of metallized capacitor film to each other, thereby forming a laminated film capacitor. In one embodiment, the laminated film capacitor may be further diced (eg, cut, cut into cubes, cut, portioned, divided, etc.) to form a die film capacitor. In one embodiment, at least one conductive layer can be applied to a die film capacitor. As recognized by those skilled in the art and with the help of the present disclosure, laminated film capacitors and die-type film capacitors are high energy density capacitors.

  In one embodiment, a capacitor comprising a capacitor film comprising a polymer composition disclosed herein comprises an automotive inverter and / or converter (eg, an inverter for a hybrid electric vehicle, a converter for a hybrid electric vehicle, an electric Inverters for automobiles, converters for electric cars, etc.).

  In one embodiment, a capacitor film produced from a polymer composition of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone, and polycarbonate composition) advantageously comprises, for example, biaxially oriented poly (propylene ) Improved electrical properties (eg BDS, Dk, Df) compared to films produced from other polymers such as (BOPP), polyphenylene sulfide (PPS), polyetheretherketone (PEEK) it can. As recognized by those skilled in the art and with the help of the present disclosure, in addition to melt processing into thin films, the proper combination of electrical properties is obtained while maintaining high temperature capacity, resulting in high energy density Is quite difficult to achieve. Dielectric films made with materials disclosed herein for capacitor film polymer compositions (eg, polyetherimide and / or polyetherimide sulfone and polycarbonate compositions) are novel and useful. This is due to such considerations. Thus, films and capacitors made from the films provide advantages for the electronics industry over current materials and methods of manufacturing components.

  In one embodiment, a capacitor film made from a polymer composition of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone, and polycarbonate composition) advantageously has a Dk that is stable to about 170 ° C. Can show. As recognized by those skilled in the art and with the help of the present disclosure, the electrical properties of the capacitor film are generally stable up to the Tg of the capacitor film.

  In one embodiment, capacitor films made from the polymer compositions of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone, and polycarbonate compositions) can advantageously be produced in a solvent-free manner. In addition, this solventless method makes it possible to manufacture such a capacitor film with high reliability on an industrial scale. In the case of conventional capacitor films, removing the solvent from the solvent-cast film can be difficult. The extruded capacitor film disclosed herein can be processed without solvent, providing both cost and manufacturing advantages, and being more environmentally friendly. In one embodiment, a capacitor film produced from a polymer composition of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone and polycarbonate composition) is advantageously a uniform film of less than about 20 microns. It can be processed by melt extrusion to thickness.

  In one embodiment, a capacitor film produced from a polymer composition of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone, and polycarbonate composition) may be, for example, polyetherimide and / or polyetherimide sulfone. An improvement in melt flow rheology can be advantageously demonstrated at the processing temperature when compared to the component itself. In general, polycarbonates have a low viscosity when compared to polyetherimide and / or polyetherimide sulfone, and thus polycarbonates, when blended together, reduce the viscosity of the polyether. Improves processability of imides and / or polyetherimide sulfones.

  In one embodiment, capacitor films made from the polymer compositions of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone, and polycarbonate compositions) are flexible compared to conventional capacitor films, While improving other advantageous physical and electrical properties, such as thinness and dielectric constant stability, advantageously both Dk and BDS improvements can be shown. In some embodiments, the capacitor films disclosed herein can have a high BDS (greater than about 600 V / micron), a high Dk (greater than about 3), and a low Df (less than about 1%). .

  In one embodiment, a capacitor film produced from a polymer composition of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone, and polycarbonate composition) is used in automotive industries (eg, electric vehicle inverters and / or Converters, DC-DC converters, AC-DC inverters, filters, circuit isolation, etc.) and any electrical / electronic applications where high operating temperature and high energy density dielectric materials are required it can. Additional advantages of capacitor films made from the polymer compositions of the present disclosure (eg, polyetherimide and / or polyetherimide sulfone, and polycarbonate compositions) may be apparent to those skilled in the art in view of the present disclosure.

  Since the subject matter has been generally described, the following examples are presented as specific embodiments of the present disclosure and to demonstrate this practice and advantages. It is understood that the examples are given by way of illustration and are not intended to limit the details of the claims that follow in any way. The following test procedures were used to evaluate various capacitor films and polymer compositions.

  The glass transition temperature (Tg) of the capacitor film is made from the polymer composition for capacitor films disclosed herein up to 300 ° C. for polyetherimide and / or polyetherimide sulfone (control / comparison). In the case of a capacitor film up to 250 ° C. and in the case of polycarbonate (control / comparison) up to 200 ° C. using a differential scanning calorimetry (DSC) at a heating rate of 20 ° C./min. Results were reported in a second scan.

  The trouser tear strength of the film samples was measured in the machine direction (MD) and the cross direction (TD) according to ASTM D1938.

  The dynamic and static coefficient of friction of the extruded film was measured according to ASTM D1894 on an aluminum surface.

  The transparency of the film was observed by visual evaluation of the film surface. The capacitor film had no visual haze or opacity.

  Extruded thin films of each material were tested for dielectric breakdown strength (BDS) using the ASTM D149 test method in GALDEN HT oil, where GALDEN HT ranges from 55 ° C to 270 ° C. Is a series of dielectric fluids having a boiling point of and are commercially available from Ideal Vacuum Products, LLC. The oil was brought to the test temperature using a hot plate / resistor coil. The electrodes consisted of 1/4 inch stainless steel balls on the bottom electrode of a 3 inch brass plate. Gradient this brass plate at 500 V / s using a Trek 30/20 ± 30 kV DC high voltage power supply until the voltage at which the material is electrically shorted and the failure was recorded by Labview computer software It was. BDS was measured at 20 ° C, 50 ° C, 100 ° C, 135 ° C and 150 ° C. Reported values represent the average of over 20 samples at each temperature and reported Weibull statistical analysis.

  The relative dielectric constant (Dk) and dielectric loss tangent (Df) were measured on a film sample by the following method. Gold of 100 nm thickness was deposited on five samples of each type of material as a top electrode with a 10 mm circular shadow mask by electron beam evaporation. The bottom electrode consisted of 100 nm thick gold over the entire area of the bottom of the sample. An Agilent E4980A Precision LCR instrument was used to measure the capacitance and dissipation factor in the applied bias field. Dk was calculated using the electrode diameter (a 10 mm diameter disk electrode was used for all electrical tests) and film thickness. The film thickness was accurately calculated as ± 0.2 μm using a Heidenhain Metro thickness gauge. The temperature of the furnace varied from -40 ° C to 150 ° C, and the LCR measuring instrument was changed at a frequency in the range of 100 Hz to 1 GHz at each temperature. The temperature of the furnace was confirmed by a thermocouple inside the furnace connected to a digital multimeter.

The characteristics of the polymer composition for a capacitor film containing polyetherimide (PEI) and / or polyetherimide sulfone (PEIS) and polycarbonate (PC) were examined. More specifically, the samples outlined in Table 1 were first compounded into pellets and then extruded into films.

  ULTEM 1010K is a PEI characterized by structure Vb. Lexan FST is a polycarbonate characterized by structure XIXc and structure XX, and 1% Si is provided by a polysiloxane unit represented by structure XXII and further characterized by structure XXIIb-2 It was done. The PEI / PEIS blend has a weight ratio of 60:40 PEI: PEIS, where PEI is characterized by structure Vb and PEIS is characterized by structure VIa. The PEPQ stabilizer is tris (2,4-di-tert-butylphenyl) phosphite. The phosphite stabilizer was tris (2,4-di-tert-butylphenyl) phosphite.

The properties of the extruded material are shown in Table 2.

  Resin blends (eg, polymer compositions for capacitor films) were easily compounded into a pellet form using biaxial and then melt extruded into films having thicknesses of 10 microns and 20 microns. The improvement in performance as a function of temperature and frequency was surprising and did not foresee the material properties of breakdown strength (BDS), dielectric constant (Dk) and dielectric loss tangent (Df). The improvement in properties significantly increases the energy density based on equation (3), where the linear law and the power law explain the relationship for Dk and BDS, respectively.

  Electrical properties of film samples prepared as described in Example 1 derived from a polymer composition for capacitor films comprising polyetherimide (PEI) and / or polyetherimide sulfone (PEIS) and polycarbonate (PC). It was investigated. More specifically, the average breaking strength (BDS) was examined.

The average BDS values of the materials tested as a function of composition, temperature and film thickness are shown in Tables 3 and 4 and graphically in FIGS.

  The BDS improvement of the 10 micron thick film from Comparative Sample A, including Sample # 1 and Sample # 2, ranged from 27 V / micron to 181 V / micron from room temperature to 150 ° C. It showed that the BDS performance was improved from 5% to 30%, and thus the energy density was improved from 10% to 69% (in equation (3), increased to the square). Furthermore, it was noted that for each sample material, a maximum value was obtained at a particular temperature, ranging from 50 ° C to 100 ° C. After reaching the maximum value, it is uncommon for the BDS of the material to decrease with increasing temperature. However, it is not expected that resin blends at two different levels will give similar results demonstrated for Sample # 1 and Sample # 2. The nonlinear response due to the composition was not expected or predicted. For the 20 micron thick film, similar results were obtained, with blends consisting of 25 wt% and 50 wt% LEXAN FST resin increasing BDS by 3% to 34%, respectively. Even when the film equivalent to LEXAN FST resin (Sample B) is superior to all of the other materials tested for BDS, such LEXAN FST resin film has the lowest temperature performance (Tg = 140 ° C.) Compared to samples # 1 and # 2, which have a high and undesired Df.

  The graphical representation in FIGS. 1 and 2 of the data reported in Tables 3 and 4 showing V / micron versus temperature for average BDS shows the dependence of BDS on the composition. Furthermore, these data strongly suggest that the addition of LEXAN FST resin to ULTEM 1010K resin improves the process, not the weight average of the constituents.

  Electrical properties of film samples prepared as described in Example 1 derived from a polymer composition for capacitor films comprising polyetherimide (PEI) and / or polyetherimide sulfone (PEIS) and polycarbonate (PC). It was investigated. More specifically, specific permittivity (Dk) and dielectric loss tangent (Df) were examined.

Dk and Df were studied as a function of temperature and frequency for 7-20 micron thick films and these data are shown in Tables # 5 (Dk) and Table # 6 (Df).

  The Dk for sample A increased to 3.07 to 2.99 with increasing temperature and frequency over the range of 20 ° C. to 150 ° C. and 100 Hz to 1 MHz, respectively. In contrast, Dk of sample # 1 demonstrated a similar trend, but under the same test conditions, it improved by an average of 5.4% and was in the range of 3.23 to 3.16. This Dk improvement is due to the addition of LEXAN FST resin and is characterized by a Dk in the range of 3.46 to 3.52 over the same temperature and frequency range. High Dk significance is a direct conversion of Dk to higher energy density, as outlined in Equation (3).

  In contrast, Df of sample # 1 was improved over sample A, ranging from 0.185% to 0.665% versus 0.153% to 0.34%, respectively. Since energy is lost during the formation of heat and causes heating of the electrical device, an increase in Df is generally considered undesirable. In each of the test samples, a material that exhibits <1% for applications over the range of frequencies of interest is blended.

Table 7 summarizes some of the properties of the capacitor film for the test samples and shows that it is useful to add LEXAN FST resin to ULTEM resin to improve dielectric performance in high temperature and high energy capacitors. Has been.

  For any US national phase application from this application, all publications and patents mentioned in this disclosure are incorporated herein by reference in their entirety, and For purposes of describing and disclosing the compositions and methods described in the publications, they are used in connection with the methods of the present disclosure. Any publications and patents discussed in this specification are provided solely for their disclosure prior to the filing date of the present application. Nothing in this specification should be construed as an admission that the inventors have accepted such disclosure by virtue of prior invention.

  In any application prior to the US Patent and Trademark Office, 37C. F. R. To satisfy the requirements of § 1.72 and 37C. F. R. § 1.72 (b), “To be able to quickly determine the nature and spirit of technical disclosure by reviewing the United States Patent Office and the public” (to enable the United States Patent and Trademark office and the public general to A summary of the present application is presented for the purposes specified in “determine quickly acuity inspection the nature and the gist of the technical disclosure”. Accordingly, the summary of the present application is not intended to be used for interpreting the scope of the claims or for limiting the scope of the subject matter disclosed herein. Furthermore, any headings that may be used herein are also not intended to be used to interpret the claims or to limit the scope of the subject matter disclosed herein. Absent. Any use of a past tense statement that describes an embodiment that is otherwise indicated as constructive or predictive reflects that the constructive or predictive embodiment has actually taken place. Not intended.

  The present disclosure is further illustrated by the following examples, which should in no way be construed as imposing limitations on the scope thereof. On the contrary, the means must be various other aspects, embodiments, modifications and equivalents thereof, and after reading the description herein, depart from the spirit of the invention or the appended claims. It will be clearly understood that it may be suggested to one skilled in the art without.

Addition of disclosure The following are non-limiting specific embodiments according to the present invention.

  A first embodiment is a uniaxially stretched high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide and poly (carbonate-arylate ester), wherein the polyetherimide is an aromatic dianhydride And a unit derived from polymerization of a diamine containing m-phenylenediamine, p-phenylenediamine or a combination thereof, and end-capped with a substituted or unsubstituted aromatic primary monoamine, Arylate ester) comprises different bisphenol carbonate repeat units and arylate ester repeat units, and the high yield extruded capacitor film is a miscible polymer blend prior to entering the extruder used to produce the capacitor film. Gross weight of Respect, including more than about 90% by weight of the miscible polymer blend into the extruder, a uniaxial stretching high yield extrusion capacitor films.

  The second embodiment is the capacitor film of the first embodiment having a thickness of about 0.1 microns to about 50 microns.

  The third embodiment is a capacitor film according to any of the first to second embodiments, having a thickness of about 0.1 microns to about 20 microns.

In a fourth embodiment, the polyetherimide has a weight average molecular weight of about 20,000 Da to about 400,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards, imide, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity of 100 sec ^-1 and 5,000Sec ^-1 is less than about 11, polyetherimide has determined according to ASTM D638, Has a tensile modulus of about 380,000 psi (2,618 MPa) or greater, and the poly (carbonate-arylate ester) is about 2,000 Da to about 100,000 Da as measured by GPC using a polycarbonate standard. It has a weight average molecular weight and is poly (car Nate-arylate ester) having any intrinsic viscosity of about 0.3 dl / g to about 1.5 dl / g as measured in chloroform at 25 ° C. The capacitor film as described, having a glass transition temperature of greater than about 170 ° C., measured in accordance with ASTM D648 at 264 psi (1.8 Mpa) in a 3.2 millimeter (mm) thick sample Then, it has a heat distortion temperature of about 150 ° C. or more, and has a relative dielectric constant of about 3 to about 5 when measured in accordance with ASTM D150 at 1 kHz, 23 ° C. and 50% relative humidity (RH). And has a dielectric loss tangent of about 0% to about 1 when measured at 1 kHz, 23 ° C. and 50% RH, and measured at 23 ° C. in accordance with ASTM D149. Having a fracture strength of about 500 V / micron to about 800 V / micron, and a film thickness of less than about +/− 10% of the film thickness relative to the average thickness of the film over a specific measurement area Having wrinkle free areas with thickness variations and having an average surface roughness (Ra) of less than about +/− 3% relative to the average film thickness as measured by optical profilometry; It is a capacitor film.

In a fifth embodiment, the polyetherimide has a weight average molecular weight of about 20,000 Da to about 400,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards, imide, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity and 5,000Sec ^-1 of 100 sec ^-1 is less than about 10, polyetherimide has determined according to ASTM D638, Has a tensile modulus of about 380,000 psi (2,618 MPa) or greater, and the poly (carbonate-arylate ester) is about 2,000 Da to about 100,000 Da as measured by GPC using a polycarbonate standard. It has a weight average molecular weight and is poly (car Nate-arylate ester) has an intrinsic viscosity of about 0.3 dl / g to about 1.5 dl / g as measured in chloroform at 25 ° C., according to any of the first to fourth embodiments The capacitor film as described, having a glass transition temperature of greater than about 190 ° C., measured in accordance with ASTM D648 at 264 psi (1.8 Mpa) in a 3.2 millimeter (mm) thick sample Then, it has a heat distortion temperature of about 170 ° C. or higher, and has a relative dielectric constant of about 3 to about 5 when measured in accordance with ASTM D150 at 1 kHz, 23 ° C. and 50% RH. Having a dielectric loss tangent of about 0.1% to about 0.5% when measured at 23 ° C. and 50% RH, and measured at 23 ° C. in accordance with ASTM D149. And a film thickness of less than about +/− 10% of the film thickness with respect to the average thickness of the film over a specific measurement area, having a breaking strength of about 600 V / micron to about 800 V / micron. A capacitor having an average surface roughness (Ra) of less than about +/− 3% relative to the average film thickness as measured by optical profilometry, having wrinkle free areas It is a film.

  The sixth embodiment has a first to fifth kinetic coefficient of friction on a metallized surface, on aluminum, and / or on its own, less than about 0.75, as measured according to ASTM D1894. It is a capacitor film in any one of embodiments.

  The seventh embodiment includes first to sixth, wherein the coefficient of static friction on the metallized surface, on aluminum, and / or on itself is less than about 0.75, as measured according to ASTM D1894. It is a capacitor film in any one of embodiments.

  In an eighth embodiment, the dielectric constant of the capacitor film at 1 kHz remains essentially unchanged from about 0 ° C. to about 170 ° C., and the relative dielectric constant ranges from about 0 ° C. to about 170 ° C. The capacitor film according to any one of the first to seventh embodiments, wherein the capacitor film varies by less than about 20% with respect to the highest relative dielectric constant value.

  The ninth embodiment has a dielectric loss tangent of the capacitor film at 1 kHz that remains essentially unchanged from about 0 ° C. to about 170 ° C., and is from about 0.1% to about 1%. It is a capacitor film in any one of embodiment.

  The tenth embodiment is that of the first to ninth embodiments, wherein the dielectric loss tangent of the capacitor film is about 0.1% to about 1% when measured from 1 kHz to 100 kHz at 23 ° C. and 50% RH. It is a capacitor film in any one.

  In an eleventh embodiment, the difference in breaking strength of the capacitor film from about 0 ° C. to about 170 ° C. is less than about 40% of the breaking strength value at 23 ° C. when measured according to ASTM D149. It is a capacitor film in any one of 10th Embodiment.

  The twelfth embodiment is any of the first to eleventh embodiments, wherein the capacitance difference at 1 kHz and from about 0 ° C. to about 170 ° C. is less than about +/− 5% relative to the capacitance value at 23 ° C. It is a capacitor film of a crab.

  The thirteenth embodiment is the capacitor film according to any of the first to twelfth embodiments, having a single glass transition temperature of about 170 ° C. or higher.

Fourteenth embodiment, in the 100 cm ² area, having a diameter greater than about 20 microns, including carbide inclusions of less than two is the capacitor film according to any one of the first 13 embodiment of the .

  The fifteenth embodiment is a capacitor film according to any of the first to fourteenth embodiments, having a film length of about 10 m to about 10,000 m and a film width of about 300 mm to about 3,000 mm. A capacitor film having no wrinkles on at least about 80% of the total surface area of the film.

  The sixteenth embodiment is a capacitor film according to any of the first to fifteenth embodiments, having a carbon / (oxygen + hydrogen) (C / (O + H)) ratio of less than about 1.25.

  The seventeenth embodiment uses a test specimen having a thickness of 20 microns and has a longitudinal trouser tear strength of about 0.5 N / mm to about 3.0 N / mm when measured according to ASTM D1938. The capacitor film according to any one of the first to sixteenth embodiments.

  An eighteenth embodiment uses a specimen having a thickness of 20 microns and has a lateral trouser tear strength of about 0.5 N / mm to about 3.0 N / mm when measured according to ASTM D1938. The capacitor film according to any one of the first to seventeenth embodiments.

  The nineteenth embodiment is the capacitor film according to any of the first to eighteenth embodiments, comprising less than about 1000 ppm of solvent relative to the total weight of the capacitor film.

（式中、Ｔは、−Ｏ−、または式−Ｏ−Ｚ−Ｏ−により表される基とすることができ、−Ｏ−または−Ｏ−Ｚ−Ｏ−基の二価結合は、３，３’、３，４’、４，３’、または４，４’位にあり、Ｚは、６〜２７個の炭素原子を有する二価芳香族炭化水素基、このハロゲン化誘導体、２〜１０個の炭素原子を有する直鎖または分岐鎖アルキレン基、このハロゲン化誘導体、３〜２０個の炭素原子を有するシクロアルキレン基、このハロゲン化誘導体、式−（Ｃ_６Ｈ_１０）_ｚ−により表される基であり、ｚは、１〜４の整数であり、Ｒは、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、またはこれらの組合せを含むジアミン残基である）により表される、第１から第１９の実施形態のいずれかに記載のキャパシターフィルムである。 In a twentieth embodiment, the polyetherimide is of formula V:

(In the formula, T can be —O— or a group represented by the formula —O—Z—O—, and the divalent bond of the —O— or —O—Z—O— group is 3 , 3 ′, 3, 4 ′, 4, 3 ′, or 4, 4 ′, and Z is a divalent aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenated derivative thereof, 2 to A linear or branched alkylene group having 10 carbon atoms, a halogenated derivative thereof, a cycloalkylene group having 3 to 20 carbon atoms, a halogenated derivative thereof, represented by the formula — (C ₆ H ₁₀ ) _z —. Wherein z is an integer from 1 to 4 and R is a diamine residue comprising m-phenylenediamine, p-phenylenediamine, or a combination thereof. It is a capacitor film in any one of 19th Embodiment.

（式中、Ｑ^ａは、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−ＳＯ_２−、−ＳＯ−または−Ｃ_ｙ〜２ｙ−、このハロゲン化誘導体であり、ｙは、１〜５の整数である）
により表される二価の基である、第２０の実施形態に記載のキャパシターフィルムである。 In a twenty-first embodiment, Z is of formula IVa:

_Wherein Q ^a is a single bond, —O—, —S—, —C (O) —, —SO ₂ —, _—SO— or —C y to _2y —, a halogenated derivative thereof, and y Is an integer from 1 to 5)
It is a capacitor film as described in 20th Embodiment which is a bivalent group represented by these.

により表される、第２０または第２１の実施形態に記載のキャパシターフィルムである。 In a twenty-second embodiment, z is the formula XI:

It is a capacitor | condenser film as described in 20th or 21st embodiment represented by these.

  A twenty-third embodiment is any of the first to twenty-second embodiments, wherein the polyetherimide comprises from about 1.0 to about 1.4 molar equivalents of anhydrous groups per 1.0 amine group. It is a capacitor film of description.

In a twenty-fourth embodiment, the substituted or unsubstituted aromatic primary monoamine comprises a substituted and unsubstituted aniline, a substituted and unsubstituted naphthyl primary amine, and a substituted and unsubstituted heteroarylamine, wherein the substituent is C _6-12 aryl group, a halogenated _{C 6 to 12} aryl _{group, C 1 to 12} alkyl group, a halogenated _{C 1 to 12} alkyl group, sulfone _{group, C 1 to 12} ester _{group, C 1 to 12} amide groups, _{halogens, C. 1 to 12} alkyl ether group, C _{6 to 12} aryl ether groups, and is selected from the group consisting of C _{6 to 12} aryl keto group attached to the aromatic ring, from a first of any one of twenty-third embodiment of the It is a capacitor film.

  A twenty-fifth embodiment is a capacitor film according to any of the first to twenty-fourth embodiments, wherein the substituted or unsubstituted aromatic primary monoamine comprises aniline.

  The twenty-sixth embodiment is the capacitor film according to any one of the first to twenty-fifth embodiments, wherein the polyetherimide further comprises polyetherimide sulfone.

  The twenty-seventh embodiment is the capacitor film of the twenty-sixth embodiment, wherein the weight ratio of polyetherimide: polyetherimide sulfone is about 99: 1 to about 30:70.

  A twenty-eighth embodiment is any of the first to twenty-seventh embodiments, wherein the polyetherimide is present in the miscible polymer blend in an amount of about 0.1 wt% to about 99.9 wt%. It is a capacitor film of description.

  A twenty-ninth embodiment according to any of the first to twenty-eighth embodiments, wherein the polyetherimide is present in the miscible polymer blend in an amount of about 50 wt% to about 99.9 wt%. It is a capacitor film.

  A thirtieth embodiment provides about 15% by weight of a polyetherimide other than a polyetherimide, wherein the polyetherimide comprises units derived from polymerization of an amine comprising m-phenylenediamine, p-phenylenediamine, or a combination thereof. It is a capacitor film in any one of the 1st to 29th embodiments containing less.

（式中、Ｒ^ａおよびＲ^ｂは、それぞれ独立して、Ｃ_１〜１２アルキル基、Ｃ_１〜１２アルケニル基、Ｃ_３〜８シクロアルキル基またはＣ_１〜１２アルコキシ基であり、ｐおよびｑは、それぞれ独立して、０〜４であり、Ｘ^ａは、２つのアリーレン基の間の架橋基であり、Ｘ^ａは、単結合、−Ｏ−、−Ｓ−、−Ｓ（Ｏ）−、−Ｓ（Ｏ）_２−、−Ｃ（Ｏ）−、式−Ｃ（Ｒ^ｃ）（Ｒ^ｄ）−であるＣ_１〜１１アルキリデン基であり、Ｒ^ｃおよびＲ^ｄは、それぞれ独立して、水素、Ｃ_１〜１０アルキル基、または式−Ｃ（＝Ｒ^ｅ）−の基であり、Ｒ^ｅは、二価Ｃ_１〜１０炭化水素基である）
により表される、第１から第３０の実施形態のいずれかに記載のキャパシターフィルムである。 In a thirty-first embodiment, the bisphenol carbonate repeating unit is of formula XII:

Wherein R ^a and R ^b are each independently a C _1-12 alkyl group, a C _1-12 alkenyl group, a C _3-8 cycloalkyl group or a C _1-12 alkoxy group, and p and q Are each independently 0 to 4, X ^a is a bridging group between two arylene groups, and X ^a is a single bond, —O—, —S—, —S (O) —. _{, -S (O) 2 -,} - C (O) -, the formula ^{-C (R c) (R d} ) - is a is _{C 1 to 11} alkylidene group, ^{R c} and ^{R d} are each independently , Hydrogen, a C _1-10 alkyl group, or a group of formula —C (═R ^e ) —, where R ^e is a divalent C _1-10 hydrocarbon group)
It is a capacitor film in any one of the 1st to 30th embodiment represented by these.

（式中、Ａｒ^１は、少なくとも１つの芳香族基を含有するＣ_６〜３２ヒドロカルビル基である）
により表される、第１から第３１の実施形態のいずれかに記載のキャパシターフィルムである。 A thirty-second embodiment, wherein the arylate ester repeat unit is of formula XVIII:

_Where Ar ¹ is a C _6-32 hydrocarbyl group containing at least one aromatic group.
It is a capacitor film in any one of the 1st to 31st embodiment represented by these.

  The thirty-third embodiment is the capacitor film according to thirty-second embodiment, wherein the at least one aromatic group comprises phenyl, naphthalene, anthracene, or a combination thereof.

（式中、ｍは約４〜約１００である）
により表されるイソフタレート−テレフタレート−レゾルシノールエステル単位を含む、第１から第３３の実施形態のいずれかに記載のキャパシターフィルムである。 In a thirty fourth embodiment, the arylate ester repeat unit is of formula XVIIIc:

(Wherein m is about 4 to about 100)
The capacitor film according to any one of the first to thirty-third embodiments, comprising an isophthalate-terephthalate-resorcinol ester unit represented by:

（式中、Ｒはそれぞれ独立して、Ｃ_１〜１３一価ヒドロカルビル基である）
により表されるシロキサン単位をさらに含む、第１から第３４の実施形態のいずれかに記載のキャパシターフィルムである。 In a thirty fifth embodiment, the poly (carbonate-arylate ester) has the formula XXII:

(In the formula, each R is independently a C _1-13 monovalent hydrocarbyl group)
The capacitor film according to any one of the first to thirty-fourth embodiments, further including a siloxane unit represented by:

  A thirty-sixth embodiment is the first to thirty-fifth embodiment, wherein the poly (carbonate-arylate ester) is present in the miscible polymer blend in an amount of about 0.1 wt% to about 99.9 wt%. It is a capacitor film in any one of.

  The thirty-seventh embodiment is any of the first to thirty-sixth embodiments, wherein the poly (carbonate-arylate ester) is present in the miscible polymer blend in an amount of about 0.1 wt% to about 50 wt%. It is a capacitor film of a crab.

  A thirty-eighth embodiment is the first to the first in which the polyetherimide and poly (carbonate-arylate ester) are each present in an amount effective to provide one glass transition temperature of the capacitor film in the miscible polymer blend. 37. The capacitor film according to any one of 37 embodiments.

  A thirty-ninth embodiment is the first to thirty-eighth aspect wherein the polyetherimide and poly (carbonate-arylate ester) are each present in an amount effective to provide a miscible polymer blend in the capacitor film polymer composition. It is a capacitor film in any one of embodiments.

  A 40th embodiment, wherein the miscible polymer blend further comprises a phosphorus-containing stabilizer in an amount of about 0 wt% to about 2 wt%, based on the total weight of the miscible polymer blend, The agent is a capacitor film according to any of the first to thirty-third embodiments, wherein the agent has a weight average molecular weight of about 500 Da or more.

  The forty-first embodiment is an article including the uniaxially stretched high-yield extruded capacitor film described in any of the first to forty embodiments.

  The forty-second embodiment is the article of the forty-first embodiment, further comprising a metal layer deposited on at least a portion of the film to form a metallized capacitor film.

  The 43rd embodiment is the article of the 42nd embodiment, wherein the metal layer comprises a conductive metal.

  A forty-fourth embodiment according to the forty-third embodiment, wherein the conductive metal comprises copper, aluminum, silver, gold, nickel, zinc, titanium, chromium, vanadium, tantalum, niobium, brass or combinations thereof. It is an article.

  A 45th embodiment is the article of any of the 42nd through 44th embodiments, wherein the metal layer has a thickness of the metal layer from about 1 angstrom to about 3,000 angstrom.

  A forty-sixth embodiment is the article according to any of the forty-second to forty-fifth embodiments, wherein the metal layer has a metal layer thickness of about 1 angstrom to about 2,820 angstrom.

  A 47th embodiment is an article according to any of the 42nd to 46th embodiments, wherein the metal layer has a resistivity of the metal layer of about 0.1 to about 100 ohms / square.

  Forty-eighth embodiment, the metal layer is vacuum metal deposition, high temperature vacuum deposition, chemical vapor deposition, atomic layer deposition, metal sputtering, plasma treatment, electron beam treatment, chemical oxidation reaction or reduction reaction, electroless wet chemical vapor deposition, Or the article according to any of the forty-second to forty-seventh embodiments, deposited on at least a portion of the film by a combination thereof.

  The 49th embodiment is an article according to any of the 42nd to 48th embodiments, wherein the metallized capacitor film is wound to form a wound metallized capacitor film.

  The 50th embodiment is a capacitor including the wound metallized film described in the 49th embodiment.

  The 51st embodiment is an electronic article including the capacitor described in the 50th embodiment.

  The 52nd embodiment is an inverter for an automobile including the capacitor described in the 50th embodiment.

  The 53rd embodiment is a converter for an automobile including the capacitor described in the 50th embodiment.

  A 54th embodiment is a uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide and poly (carbonate-arylate ester), wherein the polyetherimide is an aromatic dianhydride And a unit derived from polymerization of a diamine containing m-phenylenediamine, p-phenylenediamine or a combination thereof, and end-capped with a substituted or unsubstituted aromatic primary monoamine, Arylate ester) contains different bisphenol carbonate repeat units and arylate ester repeat units, and the high yield extruded capacitor film is solvent free and enters the extruder used to produce the capacitor film. Previous miscible poly A uniaxially stretched, high-yield extrusion comprising about 90% by weight or more of the miscible polymer blend entering the extruder and having a film thickness of about 0.1 microns to about 20 microns, based on the total weight of the blend It is a capacitor film.

  The 55th embodiment is the capacitor film of the 54th embodiment, wherein the polyetherimide further comprises polyetherimide sulfone.

  A fifty-sixth embodiment is a uniaxially stretched high-yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide sulfone and poly (carbonate-arylate ester), wherein the polyetherimide sulfone is aromatic The poly (carbonate-arylate ester) contains a unit derived from the polymerization of a dianhydride and a diamine containing diaminodiphenylsulfone and is end-capped with a substituted or unsubstituted aromatic primary monoamine. The high yield extruded capacitor film comprising carbonate repeat units and arylate ester repeat units is solvent free and contains a total of miscible polymer blends prior to entering the extruder used to produce the capacitor film. Vs. weight Te, containing more than about 90% by weight of the miscible polymer blend into the extruder, a uniaxial stretching high yield extrusion capacitor films.

  The 57th embodiment is a capacitor film according to the 56th embodiment, having a film thickness of about 0.1 microns to about 20 microns.

The 58th embodiment has a weight average molecular weight of about 20,000 Da to about 400,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards, polyetherimide sulfone, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity of 100 sec ^-1 and 5,000Sec ^-1 is less than about 11, polyetherimide sulfones are in accordance with ASTM D638 As determined, it has a tensile modulus greater than about 380,000 psi (2,618 MPa) and the poly (carbonate-arylate ester) is about 2,000 Da to about 100 as measured by GPC using a polycarbonate standard. , 1,000 Da weight average molecule And the poly (carbonate-arylate ester) has an intrinsic viscosity of from about 0.3 dl / g to about 1.5 dl / g as measured in chloroform at 25 ° C. The capacitor film of any of the embodiments having a glass transition temperature greater than about 170 ° C. and conforming to ASTM D648 at 264 psi (1.8 Mpa) in a 3.2 millimeter (mm) thick sample. And having a heat distortion temperature of about 150 ° C. or higher, and having a relative dielectric constant of about 3 to about 5 when measured in accordance with ASTM D150 at 1 kHz, 23 ° C. and 50% relative humidity (RH). And having a dielectric loss tangent of about 0% to about 1 when measured at 1 kHz, 23 ° C. and 50% RH, at ASTM D1 at 23 ° C. 9 has a breaking strength of about 500 V / micron to about 800 V / micron, and is about +/− 10 of the film thickness relative to the average thickness of the film over a specific measurement area. Having a wrinkle free area with a film thickness variation of less than%, and an average surface roughness of less than about +/− 3% relative to the average film thickness as measured by optical profilometry ( Ra) is a capacitor film.

The 59th embodiment is a method of producing a uniaxially stretched high yield extruded capacitor film according to any of the 1st to 58th embodiments, comprising:
(A) extruding a miscible polymer blend to form a high yield extruded capacitor film, wherein the high yield extruded capacitor film is used to produce the capacitor film. Comprising at least about 90% by weight of the miscible polymer blend entering the extruder, based on the total weight of the miscible polymer blend prior to entering the machine, and (b) the high yield extruded capacitor film A method comprising the steps of uniaxially stretching to form the uniaxially stretched, high yield extruded capacitor film.

The 60th embodiment is a method for producing a uniaxially stretched high yield extruded capacitor film according to any of the 1st to 59th embodiments, comprising:
(A) combining polyetherimide and poly (carbonate-arylate ester) to form a miscible polymer blend;
(B) melting and mixing the miscible polymer blend to form a molten polymer;
(C) filtering the molten polymer to remove particles greater than about 1 micron to form a filtered molten polymer;
(D) Extruding the filtered molten polymer with a flat die at a temperature of about 250 ° C. to about 500 ° C. to form a high yield extruded capacitor film, the high yield extruded capacitor The film comprises at least about 90% by weight of the miscible polymer blend entering the extruder, based on the total weight of the miscible polymer blend prior to entering the extruder used to produce the capacitor film; And (e) uniaxially stretching the high yield extruded capacitor film to form the uniaxially stretched high yield extruded capacitor film.

  The 61st embodiment is the method of the 60th embodiment, further comprising depositing a metal layer on at least a portion of the film to form a metallized capacitor film.

  The 62nd embodiment is the method of the 61st embodiment, further comprising the step of winding a metallized capacitor film to form a wound metallized capacitor film.

  The 63rd embodiment is the method according to the 61st or 62nd embodiment, further comprising laminating a metallized capacitor film to form a laminated film capacitor.

  The 64th embodiment is the method of the 63rd embodiment, further comprising the step of cutting the laminated film capacitor into a die shape to form a die film capacitor.

The 65th embodiment is a method of producing the uniaxially stretched high yield extruded capacitor film described in the 56th embodiment, comprising:
(A) extruding a miscible polymer blend to form a high yield extruded capacitor film, wherein the high yield extruded capacitor film is used to produce the capacitor film. Comprising at least about 90% by weight of the miscible polymer blend entering the extruder, based on the total weight of the miscible polymer blend prior to entering the machine, and (b) the high yield extruded capacitor film A method comprising the steps of uniaxially stretching to form the uniaxially stretched, high yield extruded capacitor film.

The 66th embodiment is a method for producing the uniaxially stretched high yield extruded capacitor film described in the 56th embodiment, comprising:
(A) combining polyetherimide sulfone and poly (carbonate-arylate ester) to form a miscible polymer blend;
(B) melting and mixing the miscible polymer blend to form a molten polymer;
(C) filtering the molten polymer to remove particles greater than about 1 micron to form a filtered molten polymer;
(D) Extruding the filtered molten polymer with a flat die at a temperature of about 250 ° C. to about 500 ° C. to form a high yield extruded capacitor film, the high yield extruded capacitor The film comprises at least about 90% by weight of the miscible polymer blend entering the extruder, based on the total weight of the miscible polymer blend prior to entering the extruder used to produce the capacitor film; And (e) uniaxially stretching the high yield extruded capacitor film to form the uniaxially stretched high yield extruded capacitor film.

  While embodiments of the present disclosure have been shown and described, modifications thereof can be made without departing from the spirit and teachings of the present invention. The embodiments and examples described herein are illustrative only and are not intended to be limiting. Numerous variations and modifications of the invention disclosed in the specification are contemplated and are within the scope of the invention.

  Accordingly, the scope of protection is not limited by the description set forth above, but is only limited by the claims that follow such scope, including all equivalents of the subject matter of the claims. . Every claim is incorporated herein as an embodiment of the present invention. Accordingly, the claims are a further description and are an addition to the detailed description of the invention. The disclosures of all patents, patent applications and publications cited herein are hereby incorporated by reference.

Claims (8)

A uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide and poly (carbonate-arylate ester) comprising:
The polyetherimide includes units derived from polymerization of an aromatic dianhydride and a diamine including m-phenylenediamine, p-phenylenediamine, or a combination thereof;
The polyetherimide is end-capped with a substituted or unsubstituted aromatic primary monoamine,
The poly (carbonate-arylate ester) includes different bisphenol carbonate repeating units and arylate ester repeating units,
The polyetherimide is present in an amount of about 50 wt% to about 99.9 wt% based on the total weight of the polymer blend;
The specific gravity of the poly (carbonate-arylate ester) is higher than the specific gravity of the polyetherimide,
The high yield extruded capacitor film is approximately about the amount of the miscible polymer blend entering the extruder relative to the total weight of the miscible polymer blend prior to entering the extruder used to produce the capacitor film. only contains more than 90% by weight,
The capacitor film has a glass transition temperature of over 170 ° C .;
The poly (carbonate-arylate ester) is represented by the following formula XIXc:

Wherein m is 10-30, and the x: m molar ratio is 90: 10-10: 90,
Formula XX below:

The resorcinol carbonate unit represented by A uniaxially stretched high-yield extruded capacitor film in which R ^h is independently a C _1-10 hydrocarbon group and n is 0-4 . The capacitor film according to claim 1,
The polyetherimide has a weight average molecular weight of about 20,000 Da to about 400,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards;
The polyether imide, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity and 5,000Sec ^-1 of 100 sec ^-1 is less than about 11,
The polyetherimide has a tensile modulus of about 380,000 psi (2,618 MPa) or greater, as determined according to ASTM D638,
The poly (carbonate-arylate ester) has a weight average molecular weight of about 2,000 Da to about 100,000 Da as measured by GPC using a polycarbonate standard;
The poly (carbonate-arylate ester) has an intrinsic viscosity of about 0.3 dl / g to about 1.5 dl / g as measured in chloroform at 25 ° C .;
The capacitor film,
3 . In a 2 millimeter (mm) thick sample, measured at 264 psi (1.8 MPa) according to ASTM D648, it has a heat distortion temperature of about 150 ° C. or higher,
When measured according to ASTM D150 at 1 kHz, 23 ° C. and 50% relative humidity (RH), it has a relative dielectric constant of about 3 to about 5;
It has a dielectric loss tangent of about 0% to about 1 when measured at 1 kHz, 23 ° C., and 50% RH, and is about 500 V / micron to about 800 V / micron when measured in accordance with ASTM D149 at 23 ° C. Has breaking strength,
Having wrinkle free areas with a film thickness variation of less than about +/− 10% of the film thickness relative to the average thickness of the film over a specific measurement area;
A capacitor film having an average surface roughness (Ra) of less than about +/− 3% relative to the average film thickness as measured by optical profilometry. The capacitor film according to claim 1,
The polyetherimide has a weight average molecular weight of about 20,000 Da to about 400,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards;
The polyether imide, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity of 100 sec ^-1 and 5,000Sec ^-1 is less than about 10,
The polyetherimide has a tensile modulus of about 380,000 psi (2,618 MPa) or greater, as determined according to ASTM D638,
The poly (carbonate-arylate ester) has a weight average molecular weight of about 2,000 Da to about 100,000 Da as measured by GPC using a polycarbonate standard;
The poly (carbonate-arylate ester) has an intrinsic viscosity of about 0.3 dl / g to about 1.5 dl / g when measured in chloroform at 25 ° C.
The capacitor film is
Having a glass transition temperature greater than about 190 ° C .;
In a 3.2 millimeter (mm) thick sample, measured at 264 psi (1.8 MPa) according to ASTM D648, it has a heat distortion temperature of about 170 ° C. or higher,
Having a relative dielectric constant of about 3 to about 5 when measured in accordance with ASTM D150 at 1 kHz, 23 ° C. and 50% RH;
Having a dielectric loss tangent of about 0.1% to about 0.5% when measured at 1 kHz, 23 ° C. and 50% RH;
Having a fracture strength of about 600 V / micron to about 800 V / micron measured at 23 ° C. according to ASTM D149,
Having wrinkle free areas with a film thickness variation of less than about +/− 10% of the film thickness relative to the average thickness of the film over a specific measurement area;
A capacitor film having an average surface roughness (Ra) of less than about +/− 3% relative to the average film thickness as measured by optical profilometry. A coefficient of dynamic friction on a metallized surface, on aluminum, and / or on itself is less than about 0.75, as measured according to ASTM D1894;
A coefficient of static friction on the metallized surface, on aluminum, and / or on itself, as measured according to ASTM D1894, is less than about 0.75;
The dielectric constant of the capacitor film at 1 kHz remains essentially unchanged from about 0 ° C. to about 170 ° C., and the relative dielectric constant is the highest ratio within the temperature range of about 0 ° C. to about 170 ° C. A variation of less than about 20% relative to the value of the dielectric constant;
The dielectric loss tangent of the capacitor film at 1 kHz remains essentially unchanged from about 0 ° C. to about 170 ° C., being from about 0.1% to about 1%;
The dielectric loss tangent of the capacitor film is about 0.1% to about 1% when measured at 23 ° C. and 50% RH from 1 kHz to 100 kHz.
The difference in breaking strength of the capacitor film from about 0 ° C. to about 170 ° C. is less than about 40% of the breaking strength value at 23 ° C. when measured according to ASTM D149.
The capacitance difference at 1 kHz and from about 0 ° C. to about 170 ° C. is less than about +/− 5% relative to the capacitance value at 23 ° C .;
Including less than two carbonized inclusions having a diameter greater than about 20 microns in an area of 100 cm ² ;
2. The capacitor film of claim 1 having a film length of about 10 m to about 10,000 m and a film width of about 300 mm to about 3,000 mm, wherein at least about 80% of the total surface area of the film is free of wrinkles. ,
Having a carbon / (oxygen + hydrogen) (C / (O + H)) ratio of less than about 1.25;
Having a longitudinal trouser tear strength of about 0.5 N / mm to about 3.0 N / mm when measured in accordance with ASTM D1938 using a specimen having a thickness of 20 microns;
Having a lateral trouser tear strength of about 0.5 N / mm to about 3.0 N / mm when measured in accordance with ASTM D1938 using a specimen having a thickness of 20 microns;
Containing less than about 1000 ppm of solvent relative to the total weight of the capacitor film;
The capacitor film according to claim 1, comprising at least one of the following. A uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide and poly (carbonate-arylate ester) comprising:
The polyetherimide includes units derived from polymerization of an aromatic dianhydride and a diamine including m-phenylenediamine, p-phenylenediamine, or a combination thereof;
The polyetherimide is end-capped with a substituted or unsubstituted aromatic primary monoamine,
The poly (carbonate-arylate ester) includes different bisphenol carbonate repeating units and arylate ester repeating units,
The polyetherimide is present in an amount of about 50 wt% to about 99.9 wt% based on the total weight of the polymer blend;
The specific gravity of the poly (carbonate-arylate ester) is higher than the specific gravity of the polyetherimide,
The high-yield extruded capacitor film is solvent free and enters the extruder relative to the total weight of the miscible polymer blend before entering the extruder used to make the capacitor film. comprises more than about 90% by weight of a miscible polymer blend, have a film thickness of about 0.1 microns to about 20 microns,
The capacitor film has a glass transition temperature of over 170 ° C .;
The poly (carbonate-arylate ester) is represented by the following formula XIXc:

Wherein m is 10-30, and the x: m molar ratio is 90: 10-10: 90,
Formula XX below:

The resorcinol carbonate unit represented by A uniaxially stretched high-yield extruded capacitor film in which R ^h is independently a C _1-10 hydrocarbon group and n is 0-4 . The capacitor film according to claim 5 , wherein the polyetherimide further comprises polyetherimide sulfone. A uniaxially stretched, high yield extruded capacitor film comprising a miscible polymer blend comprising polyetherimide sulfone and poly (carbonate-arylate ester),
The polyetherimide sulfone comprises units derived from the polymerization of an aromatic dianhydride and a diamine containing diaminodiphenyl sulfone,
The polyetherimide sulfone is end-capped with a substituted or unsubstituted aromatic primary monoamine,
The polyetherimide is present in an amount of about 50 wt% to about 99.9 wt% based on the total weight of the polymer blend;
The specific gravity of the poly (carbonate-arylate ester) is higher than the specific gravity of the polyetherimide,
The poly (carbonate-arylate ester) includes different bisphenol carbonate repeating units and arylate ester repeating units, and the high-yield extruded capacitor film is solvent-free and is used to produce the capacitor film. that the total weight of the previous miscible polymer blend into the extruder, viewed contains more than about 90% by weight of the miscible polymer blend into the extruder,
The capacitor film has a glass transition temperature of over 170 ° C .;
The poly (carbonate-arylate ester) is represented by the following formula XIXc:

Wherein m is 10-30, and the x: m molar ratio is 90: 10-10: 90,
Formula XX below:

The resorcinol carbonate unit represented by A uniaxially stretched high-yield extruded capacitor film in which R ^h is independently a C _1-10 hydrocarbon group and n is 0-4 . The capacitor film according to claim 7 ,
The polyetherimide sulfone has a weight average molecular weight of about 20,000 Da to about 400,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards;
The polyetherimide sulfone, as measured by capillary rheometry at 340 ° C., the ratio of the viscosity of the viscosity and 5,000Sec ^-1 of 100 sec ^-1 is less than about 11,
The polyetherimide sulfone has a tensile modulus of about 380,000 psi (2,618 MPa) or greater, as determined according to ASTM D638.
The poly (carbonate-arylate ester) has a weight average molecular weight of about 2,000 Da to about 100,000 Da as measured by GPC using a polycarbonate standard;
The poly (carbonate-arylate ester) has an intrinsic viscosity of about 0.3 dl / g to about 1.5 dl / g as measured in chloroform at 25 ° C .;
The capacitor film is
Having a glass transition temperature greater than about 170 ° C .;
In a 3.2 millimeter (mm) thick sample, measured at 264 psi (1.8 MPa) according to ASTM D648, it has a heat distortion temperature of about 150 ° C. or higher,
When measured according to ASTM D150 at 1 kHz, 23 ° C. and 50% relative humidity (RH), it has a relative dielectric constant of about 3 to about 5;
Having a dielectric loss tangent of about 0% to about 1 when measured at 1 kHz, 23 ° C. and 50% RH;
Having a fracture strength of about 500 V / micron to about 800 V / micron, measured at 23 ° C. according to ASTM D149,
Having wrinkle free areas with a film thickness variation of less than about +/− 10% of the film thickness relative to the average thickness of the film over a specific measurement area;
A capacitor film having an average surface roughness (Ra) of less than about +/− 3% relative to the average film thickness as measured by optical profilometry.

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